Personal care compositions comprising a zinc containing material in an aqueous surfactant composition

ABSTRACT

Disclosed are compositions comprising an effective amount of a zinc containing material having an aqueous solubility within the composition of less than about 25% by weight at 25° C.; from about 5% to about 50% of a surfactant; and from about 40% to about 95% water; wherein the pH of the composition is greater than about 7. Further disclosed are compositions comprising an effective amount of a zinc containing material having an aqueous solubility within the composition of less than about 25% by weight at 25° C.; from about 5% to about 50% of a surfactant; and from about 0.1% to about 5% of a zinc ionophoric material; from about 40% to about 95% water; and wherein the pH of the composition is greater than about 7.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.10/392,422, filed Mar. 18, 2003, which claims the benefit of U.S.Application Ser. No. 60/374, 346, filed Apr. 22, 2002.

FIELD OF THE INVENTION

Certain embodiments of the present invention relate to personal carecompositions and methods of treating microbial and fungal infections onthe skin or scalp. Additionally, certain embodiments of the presentinvention relate to methods for the treatment of dandruff andcompositions which provide improved anti-dandruff activity.

BACKGROUND OF THE INVENTION

Of the trace metals, zinc is the second most abundant metal in the humanbody, catalyzing nearly every bio-process directly or indirectly throughinclusion in many different metalloenzymes. The critical role zinc playscan be discerned from the symptoms of dietary deficiency, which includedermatitis, anorexia, alopecia and impaired overall growth. Zinc appearsespecially important to skin health and has been used (typically in theform of zinc oxide or calamine) for over 3000 years to control a varietyof skin problems. Recent data more specifically points to the healingand repairing properties of topical zinc treatment to damaged skin,often resulting in increased rates of healing. There is a growing bodyof biochemical support for this phenomenon. Since dandruff has beenpreviously shown to represent significant damage to scalp skin, topicalzinc treatment could aid in the repair process.

Inorganic salts, such as zinc oxide, have been employed asbacteriostatic and/or fungistatic compounds in a large variety ofproducts including paints, coatings and antiseptics. However, zinc saltsdo not possess as high of a level of biocidal efficacy as might bedesired for many anti-dandruff and skin care applications.

While the prior art may have addressed some of the problems of chivyingthe use of inorganic salts in a large variety of products, they have notaddressed the problems to the extent of or in the manner of the presentinvention. Therefore, there is a need for an improved personal carecomposition comprising a zinc containing material in an aqueoussurfactant composition.

SUMMARY OF THE INVENTION

An embodiment of the present invention is directed to a compositioncomprising an effective amount of a zinc containing material having anaqueous solubility within the composition of less than about 25% byweight at 25° C.; from about 5% to about 50% of a surfactant; and fromabout 40% to about 95% water; wherein the pH of the composition isgreater than about 7.

An additional embodiment of the present invention is directed to acomposition comprising an effective amount of a zinc containing materialhaving an aqueous solubility within the composition of less than about25% by weight at 25° C.; from about 5% to about 50% of a surfactant; andfrom about 0.1% to about 5% of a zinc ionophoric material; from about40% to about 95% water; and wherein the pH of the composition is greaterthan about 7.

These and other features, aspects, and advantages of the presentinvention will become evident to those skilled in the art from a readingof the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the relationship between pH and percent (%)soluble zinc.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

It has now surprisingly been found, in accordance with the presentinvention, that anti-dandruff efficacy can be dramatically increased intopical compositions by the use of polyvalent metal salts of pyrithione,such as zinc pyrithione, in combination with zinc containing material.Therefore an embodiment of the present invention provides topicalcompositions with improved benefits to the skin and scalp (e.g.,improved antidandruff efficacy).

An embodiment of the present invention provides a stable composition forzinc containing material (e.g., zinc oxide) dispersion where the zinccontaining material resides in a particulate form. It has been shown tobe challenging to formulate aqueous systems containing a zinc containingmaterial such as zinc oxide, due to their unique physical and chemicalproperties. They have a high density (i.e. 3 g/cm3), and needs to beevenly dispersed throughout the product so it will not aggregate orsettle. They also have a very-reactive surface chemistry as well as thepropensity to dissolve in systems with pH values below 7.5. This hasprovided a unique understanding concerning the need to control protonsources or other reactive/coordinating species (e.g., EDTA, citrate).

An embodiment of the present invention is directed toward a compositioncomprising an effective amount of a zinc containing material having anaqueous solubility within the composition of less than about 25% byweight at 25° C.; from about 5% to about 50% of a surfactant; and fromabout 40% to about 95% water; wherein the pH of the composition isgreater than about 7.

Another embodiment of the present invention is directed toward acomposition comprising an effective amount of a zinc containing materialhaving an aqueous solubility within the composition of less than about25% by weight at 25° C.; from about 5% to about 50% of a surfactant; andfrom about 0.1% to about 5% of a zinc ionophoric material; from about40% to about 95% water; and wherein the pH of the composition is greaterthan about 7.

An embodiment of the present invention is directed toward a compositioncomprising labile zinc maintained by choice of an effective zinccontaining material or formation of an effective zinc containingmaterial in situ.

An embodiment of the present invention provides topical skin and/or haircompositions which provide superior benefits from zinc oxide. Anembodiment of the present invention also provides a method for cleansingthe hair and/or skin. These, and other benefits, will become readilyapparent from the detailed description.

An embodiment of the present invention provides topical skin and/or haircompositions which provide superior benefits from zinc hydroxycarbonate.An embodiment of the present invention also provides a method forcleansing the hair and/or skin. These, and other benefits, will becomereadily apparent from the detailed description.

The present invention can comprise, consist of, or consist essentiallyof the essential elements and limitations of the invention describedherein, as well any of the additional or optional ingredients,components, or limitations described herein.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include carriers or by-products thatmay be included in commercially available materials.

The components and/or steps, including those which may optionally beadded, of the various embodiments of the present invention, aredescribed in detail below.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

All ratios are weight ratios unless specifically stated otherwise.

All temperatures are in degrees Celsius, unless specifically statedotherwise.

Except as otherwise noted, all amounts including quantities,percentages, portions, and proportions, are understood to be modified bythe word “about”, and amounts are not intended to indicate significantdigits.

Except as otherwise noted, the articles “a”, “an”, and “the” mean “oneor more”

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. The compositionsand methods/processes of the present invention can comprise, consist of,and consist essentially of the essential elements and limitations of theinvention described herein, as well as any of the additional or optionalingredients, components, steps, or limitations described herein.

Herein, “effective” means an amount of a subject active high enough toprovide a significant positive modification of the condition to betreated. An effective amount of the subject active will vary with theparticular condition being treated, the severity of the condition, theduration of the treatment, the nature of concurrent treatment, and likefactors.

A. ZINC CONTAINING MATERIAL

The composition of the present invention includes an effective amount ofa zinc containing material. Herein “zinc containing material” or ZCMmeans a material comprising zinc bound covalently, and/or ionically, orphysically by a host material.

Preferred embodiments of the present invention include an effectiveamount of a zinc containing material having an aqueous solubility withinthe composition of less than about 25%, by weight, at 25° C., morepreferably less than about 20%; more preferably less than about 15%.

Preferred embodiments of the present invention include from 0.001% to10% of a zinc containing material; more preferably from 0.01% to 5%;more preferably still from 0.1% to 3%.

In a preferred embodiment, the zinc containing material has an averageparticle size of from 100 nm to 30 μm.

Examples of zinc containing materials useful in certain embodiments ofthe present invention include the following:

Inorganic Materials. Zinc aluminate, Zinc carbonate, Zinc oxide andmaterials containing zinc oxide (i.e., calamine), Zinc phosphates (i.e.,orthophosphate and pyrophosphate), Zinc selenide, Zinc sulfide, Zincsilicates (i.e., ortho- and meta-zinc silicates), Zinc silicofluoride,Zinc Borate, Zinc hydroxide and hydroxy sulfate, zinc-containing layeredmaterials and combinations thereof.

Further, layered structures are those with crystal growth primarilyoccurring in two dimensions. It is conventional to describe layerstructures as not only those in which all the atoms are incorporated inwell-defined layers, but also those in which there are ions or moleculesbetween the layers, called gallery ions (A. F. Wells “StructuralInorganic Chemistry” Clarendon Press, 1975). Zinc-containing layeredmaterials (ZLM's) may have zinc incorporated in the layers and/or asmore labile components of the gallery ions.

Many ZLM's occur naturally as minerals. Common examples includehydrozincite (zinc carbonate hydroxide), basic zinc carbonate,aurichalcite (zinc copper carbonate hydroxide), rosasite (copper zinccarbonate hydroxide) and many related minerals that are zinc-containing.Natural ZLM's can also occur wherein anionic layer species such asclay-type minerals (e.g., phyllosilicates) contain ion-exchanged zincgallery ions. All of these natural materials can also be obtainedsynthetically or formed in situ in a composition or during a productionprocess.

Another common class of ZLM's, which are often, but not always,synthetic, is layered doubly hydroxides, which are generally representedby the formula [M²⁺ _(1-x)M³⁺ _(x)(OH)₂]^(x+)A^(m−) _(x/m)·nH₂O and someor all of the divalent ions (M²⁺) would be represented as zinc ions(Crepaldi, E L, Pava, P C, Tronto, J, Valim, J B J. Colloid Interfac.Sci. 2002, 248, 429-42).

Yet another class of ZLM's can be prepared called hydroxy double salts(Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem.1999, 38, 4211-6). Hydroxy double salts can be represented by thegeneral formula [M²⁺ _(1-x)M²⁺ _(1+x)(OH)_(3(1-y))]⁺A^(n−)_((1=3y)/n)·H₂O where the two metal ion may be different; if they arethe same and represented by zinc, the formula simplifies to[Zn_(1+x)(OH)₂]^(2x+)2×A⁻·nH₂O. This latter formula represents (wherex=0.4) common materials such as zinc hydroxychloride and zinchydroxynitrate. These are related to hydrozincite as well wherein thedivalent anion is replaced by a monovalent anion. These materials canalso be formed in situ in a composition or in or during a productionprocess.

These classes of ZLM's represent relatively common examples of thegeneral category and are not intended to be limiting as to the broaderscope of materials which fit this definition.

Natural Zinc containing materials/Ores and Minerals. Sphalerite (zincblende), Wurtzite, Smithsonite, Franklinite, Zincite, Willemite,Troostite, Hemimorphite and combinations thereof.

Organic Salts: Zinc fatty acid salts (i.e., caproate, laurate, oleate,stearate, etc.), Zinc salts of alkyl sulfonic acids, Zinc naphthenate,Zinc tartrate, Zinc tannate, Zinc phytate, Zinc monoglycerolate, Zincallantoinate, Zinc urate, Zinc amino acid salts (i.e., methionate,phenylalinate, tryptophanate, cysteinate, etc) and combinations thereof.

Polymeric Salts: Zinc polycarboxylates (i.e., polyacrylate), Zincpolysulfate and combinations thereof.

Physically Adsorbed Forms: Zinc-loaded ion exchange resins, Zincadsorbed on particle surfaces, Composite particles in which zinc saltsare incorporated, (i.e., as core/shell or aggregate morphologies) andcombinations thereof.

Zinc Salts: zinc oxalate, zinc tannate, zinc tartrate, zinc citrate,zinc oxide, zinc carbonate, zinc hydroxide, zinc oleate, zinc phosphate,zinc silicate, zinc stearate, zinc sulfide, zinc undecylate, and thelike, and mixtures thereof, preferably zinc oxide or zinc carbonatebasic.

Commercially available sources of zinc oxide include Z-Cote and Z-CoteHPI (BASF), and USP I and USP II (Zinc Corporation of America).

Commercially available sources of zinc carbonate include Zinc CarbonateBasic (Cater Chemicals: Bensenville, Ill., USA), Zinc Carbonate(Shepherd Chemicals: Norwood, Ohio, USA), Zinc Carbonate (CPS UnionCorp.: New York, N.Y., USA), Zinc Carbonate (Elementis Pigments: Durham,UK), and Zinc Carbonate AC (Bruggemann Chemical: Newtown Square, Pa.,USA).

Zinc Salts That Become Insoluble Above a pH of 7: zinc acetate, zincchloride, zinc bromide, zinc fluoride, zinc iodide, zinc sulfate, zinccitrate, zinc lactate, zinc nitrate, zinc propionate, zinc salicylate,zinc tartrate, zinc valerate, zinc gluconate, zinc selenate, zincbenzoate, zinc borate, zinc bromate, zinc formate, zincglycerophosphate, zinc picrate, zinc butyrate, and the like, andcombinations thereof.

Definition of ZCM Solubility: A zinc containing material with asolubility of less than 25% will have a measurable % soluble zinc valuebelow a threshold value determined by the weight percent and molecularweight of the zinc compound. The theoretical threshold value can becalculated by the following equation (see examples in the Table):

$\frac{0.25*{wt}\mspace{14mu} \% \mspace{14mu} {Zn}\mspace{14mu} {Compound}\mspace{14mu} {in}\mspace{14mu} {Compositon}*{moles}\mspace{14mu} {of}\mspace{14mu} {Zinc}\mspace{14mu} {in}\mspace{14mu} {Compound}*65.39\left( {{MW}\mspace{14mu} {of}\mspace{14mu} {Zn}} \right)}{{MW}\mspace{14mu} {of}\mspace{14mu} {Zn}\mspace{14mu} {Compound}}$% Zn % soluble Zn⁺²; Zinc Compound in (if 25 wt.% of zinc CompoundFormula Composition source is soluble)* Zinc Oxide ZnO 1.0% 0.20% ZincCarbonate Zn₅(CO₃)₂(OH)₆ 1.0% 0.15% Basic (Hydrozincite) Zinc StearateZn(C₁₈H₃₅O₂)₂ 1.0% 0.026%

B. ZINC IONOPHORIC MATERIAL (ZIM)

In another embodiment of the present invention, the composition furtherincludes a zinc ionophoric material. Herein, “zinc ionophoric material”and “ZIM” means a material which is or forms a hydrophobic moleculecapable of increasing cell permeability to zinc ions (i.e., exhibitingzinc ionophoric behavior). Without being bound by theory, it is believedthat ZIMs shield the charge of the zinc ion to be transported, enablingit to penetrate the hydrophobic interior of the lipid bilayer. ZIMs maybe channel-forming ionophores or mobile ion carriers. ZIMs may be thosecommonly known as zinc ionophores or those that are hydrophobic zincchelators that possess zinc ionophoric behavior. Hydrophobic zincchelators are materials that bind zinc and increase hydrophobicity ofzinc ions such that, for example, it will partition into non-aqueoussolvents. ZIMs can be effective including zinc being present in thecomposition or zinc being available within the system wherein a ZIM ispresent, yet preferred ZIMs contain zinc ions; i.e., zinc salt forms ofmaterials exhibiting zinc ionophoric behavior.

Preferred embodiments include from 0.01% to 5% of a ZIM; more preferablyfrom 0.1% to 2%.

In embodiments having a zinc containing material and a ZIM, the ratio ofzinc containing material to ZIM is preferably from 5:100 to 5:1; morepreferably from about 2:10 to 3:1; more preferably still from 1:2 to2:1.

In preferred embodiments of the present invention, the ZIM has a potencyagainst target microorganisms such that the minimum inhibitoryconcentration (“MIC”) is below 5000 parts per million. The MIC is ameasurement well understood by those skilled in the art and isindicative of anti-fungal efficacy. Generally, the lower the value ofthe composition, the better its anti-fungal efficacy, due to increasedinherent ability of the anti-dandruff agent to inhibit the growth ofmicroorganisms. The lowest tested dilution of anti-microbial active thatyields no growth is defined as the MIC.

Examples of ZIMs useful in embodiments of the present invention includethe following:

Class Name (Synonyms) Structure Bio-molecules,PeptidesandNaturallyOccurringMaterials andderivatives thereofhavingzincionophoricbehavior Lasalocid (X537A)

A23187(Calcimycin)

4-Br A23187

Ionomycin

Cyclosporin A Cyclic undecapeptide:cyclo-(MeBMT-Abu-Sar-MeLeu-Val-MeLeu-Ala-D-Ala-MeLeu-MeLeu-MeVal)Hydroxyquinolines Diodoquin(Iodoquinol; 5,7-Diiodo-8-hydroxyquinoline)

Enterovioform(Iodochlorohydroxyquinoline;5-Cl, 7-I-8-hydroxyquinoline)

Sterosan(Chloroquinaldol; 2-Me, 5,7-Dichloro-8-hydroxyquinoline)

5-7-Bibromo-8-hydroxyquinoline

Sulfur-BasedCompounds Tetra-n-butylthiuram Disulfide(TBTDS)

TransportEnhancers Albumin, histidine,arachidonic acid, picolinicacid,dihydroxyvitaminD₃, ethylmaltol

In a preferred embodiment, the ZIM is pyrithione or a polyvalent metalsalt of pyrithione. Any form of polyvalent metal pyrithione salts may beused, including platelet and needle structures. Preferred salts for useherein include those formed from the polyvalent metals magnesium,barium, bismuth, strontium, copper, zinc, cadmium, zirconium andmixtures thereof, more preferably zinc. Even more preferred for useherein is the zinc salt of 1-hydroxy-2-pyridinethione (known as “zincpyrithione” or “ZPT”); more preferably ZPT in platelet particle form,wherein the particles have an average size of up to about 20 μm,preferably up to about 5 μm, more preferably up to about 2.5 μm.

Pyridinethione anti-microbial and anti-dandruff agents are described,for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No. 3,236,733; U.S.Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat. No. 4,345,080;U.S. Pat. No. 4,323,683; U.S. Pat. No. 4,379,753; and U.S. Pat. No.4,470,982.

It is further contemplated that when ZPT is used as the anti-microbialparticulate in the anti-microbial compositions herein, that anadditional benefit of hair growth or re-growth may be stimulated orregulated, or both, or that hair loss may be reduced or inhibited, orthat hair may appear thicker or fuller.

Zinc pyrithione may be made by reacting 1-hydroxy-2-pyridinethione(i.e., pyrithione acid) or a soluble salt thereof with a zinc salt (e.g.zinc sulfate) to form a zinc pyrithione precipitate, as illustrated inU.S. Pat. No. 2,809,971.

C. TOPICAL CARRIER

In a preferred embodiment, the composition of the present invention isin the form of a topical compositions, which includes a topical carrier.Preferably, the topical carrier is selected from a broad range oftraditional personal care carriers depending on the type of compositionto be formed. By suitable selections of compatible carriers, it iscontemplated that such a composition is prepared in the form of dailyskin or hair products including conditioning treatments, cleansingproducts, such as hair and/or scalp shampoos, body washes, handcleansers, water-less hand sanitizer/cleansers, facial cleansers and thelike.

In a preferred embodiment, the carrier is water. Preferably thecompositions of the present invention comprise from 40% to 95% water byweight of the composition; preferably from 50% to 85%, more preferablystill from 60% to 80%.

D. DETERSIVE SURFACTANT

The composition of the present invention includes a detersivesurfactant. The detersive surfactant component is included to providecleaning performance to the composition. The detersive surfactantcomponent in turn comprises anionic detersive surfactant, zwitterionicor amphoteric detersive surfactant, or a combination thereof. Suchsurfactants should be physically and chemically compatible with theessential components described herein, or should not otherwise undulyimpair product stability, aesthetics or performance.

Suitable anionic detersive surfactant components for use in thecomposition herein include those which are known for use in hair care orother personal care cleansing compositions. The concentration of theanionic surfactant component in the composition should be sufficient toprovide the desired cleaning and lather performance, and generally rangefrom about 5% to about 50%, preferably from about 8% to about 30%, morepreferably from about 10% to about 25%, even more preferably from about12% to about 22%.

Preferred anionic surfactants suitable for use in the compositions arethe alkyl and alkyl ether sulfates. These materials have the respectiveformulae ROSO₃M and RO(C₂H₄O)_(x)SO₃M, wherein R is alkyl or alkenyl offrom about 8 to about 18 carbon atoms, x is an integer having a value offrom 1 to 10, and M is a cation such as ammonium, alkanolamines, such astriethanolamine, monovalent metals, such as sodium and potassium, andpolyvalent metal cations, such as magnesium, and calcium.

Preferably, R has from about 8 to about 18 carbon atoms, more preferablyfrom about 10 to about 16 carbon atoms, even more preferably from about12 to about 14 carbon atoms, in both the alkyl and alkyl ether sulfates.The alkyl ether sulfates are typically made as condensation products ofethylene oxide and monohydric alcohols having from about 8 to about 24carbon atoms. The alcohols can be synthetic or they can be derived fromfats, e.g., coconut oil, palm kernel oil, tallow. Lauryl alcohol andstraight chain alcohols derived from coconut oil or palm kernel oil arepreferred. Such alcohols are reacted with between about 0 and about 10,preferably from about 2 to about 5, more preferably about 3, molarproportions of ethylene oxide, and the resulting mixture of molecularspecies having, for example, an average of 3 moles of ethylene oxide permole of alcohol, is sulfated and neutralized.

Other suitable anionic detersive surfactants are the water-soluble saltsof organic, sulfuric acid reaction products conforming to the formula[R¹—SO₃-M] where R¹ is a straight or branched chain, saturated,aliphatic hydrocarbon radical having from about 8 to about 24,preferably about 10 to about 18, carbon atoms; and M is a cationdescribed hereinbefore.

Still other suitable anionic detersive surfactants are the reactionproducts of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil or palm kernel oil; sodium or potassium salts of fattyacid amides of methyl tauride in which the fatty acids, for example, arederived from coconut oil or palm kernel oil. Other similar anionicsurfactants are described in U.S. Pat. Nos. 2,486,921; 2,486,922; and2,396,278.

Other anionic detersive surfactants suitable for use in the compositionsare the succinnates, examples of which include disodiumN-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammoniumlauryl sulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester ofsodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;and dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic detersive surfactants include olefin sulfonateshaving about 10 to about 24 carbon atoms. In addition to the true alkenesulfonates and a proportion of hydroxy-alkanesulfonates, the olefinsulfonates can contain minor amounts of other materials, such as alkenedisulfonates depending upon the reaction conditions, proportion ofreactants, the nature of the starting olefins and impurities in theolefin stock and side reactions during the sulfonation process. A nonlimiting example of such an alpha-olefin sulfonate mixture is describedin U.S. Pat. No. 3,332,880.

Another class of anionic detersive surfactants suitable for use in thecompositions are the beta-alkyloxy alkane sulfonates. These surfactantsconform to the formula

where R¹ is a straight chain alkyl group having from about 6 to about 20carbon atoms, R² is a lower alkyl group having from about 1 to about 3carbon atoms, preferably 1 carbon atom, and M is a water-soluble cationas described hereinbefore.

Preferred anionic detersive surfactants for use in the compositionsinclude sodium lauryl sulfate, sodium laureth sulfate, triethylaminelauryl sulfate, triethylamine laureth sulfate, triethanolamine laurylsulfate, triethanolamine laureth sulfate, monoethanolamine laurylsulfate, monoethanolamine laureth sulfate, diethanolamine laurylsulfate, diethanolamine laureth sulfate, ammonium lauryl sulfate,ammonium laureth sulfate, lauric monoglyceride sodium sulfate, potassiumlauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate,sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammoniumcocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodiumlauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate, and combinations thereof. Most preferred anionicdetersive surfactants include sodium lauryl sulfate and sodium laurethsulfate.

Suitable amphoteric or zwitterionic detersive surfactants for use in thecomposition herein include those which are known for use in hair care orother personal care cleansing. Concentration of such amphotericdetersive surfactants preferably ranges from about 0.5% to about 20%,preferably from about 1% to about 10%. Non limiting examples of suitablezwitterionic or amphoteric surfactants are described in U.S. Pat. Nos.5,104,646 (Bolich Jr. et al.), 5,106,609 (Bolich Jr. et al.).

Amphoteric detersive surfactants suitable for use in the composition arewell known in the art, and include those surfactants broadly describedas derivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight or branched chain and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic group such as carboxy, sulfonate,sulfate, phosphate, or phosphonate. Preferred amphoteric detersivesurfactants for use in the present invention include cocoamphoacetate,cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate, and mixturesthereof.

Zwitterionic detersive surfactants suitable for use in the compositionare well known in the art, and include those surfactants broadlydescribed as derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic group such as carboxy, sulfonate, sulfate, phosphate orphosphonate. Zwitterionics such as betaines are preferred.

The compositions of the present invention may further compriseadditional surfactants for use in combination with the anionic detersivesurfactant component described hereinbefore. Suitable optionalsurfactants include nonionic and cationic surfactants. Any suchsurfactant known in the art for use in hair or personal care productsmay be used, provided that the optional additional surfactant is alsochemically and physically compatible with the essential components ofthe composition, or does not otherwise unduly impair productperformance, aesthetics or stability. The concentration of the optionaladditional surfactants in the composition may vary with the cleansing orlather performance desired, the optional surfactant selected, thedesired product concentration, the presence of other components in thecomposition, and other factors well known in the art.

Non limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the compositions aredescribed in McCutcheon's, Emulsifiers and Detergents, 2002 Annual,published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678,2,658,072; 2,438,091; 2,528,378.

E. DISPERSED PARTICLES

The composition of the present invention may include dispersedparticles. In the compositions of the present invention, it ispreferable to incorporate at least 0.025% by weight of the dispersedparticles, more preferably at least 0.05%, still more preferably atleast 0.1%, even more preferably at least 0.25%, and yet more preferablyat least 0.5% by weight of the dispersed particles. In the compositionsof the present invention, it is preferable to incorporate no more thanabout 20% by weight of the dispersed particles, more preferably no morethan about 10%, still more preferably no more than 5%, even morepreferably no more than 3%, and yet more preferably no more than 2% byweight of the dispersed particles.

F. AQUEOUS CARRIER

The compositions of the present invention are typically in the form ofpourable liquids (under ambient conditions). The compositions willtherefore typically comprise an aqueous carrier, which is present at alevel of from about 20% to about 95%, preferably from about 60% to about85%. The aqueous carrier may comprise water, or a miscible mixture ofwater and organic solvent, but preferably comprises water with minimalor no significant concentrations of organic solvent, except as otherwiseincidentally incorporated into the composition as minor ingredients ofother essential or optional components.

G. ADDITIONAL COMPONENTS

The compositions of the present invention may further comprise one ormore optional components known for use in hair care or personal careproducts, provided that the optional components are physically andchemically compatible with the essential components described herein, ordo not otherwise unduly impair product stability, aesthetics orperformance. Individual concentrations of such optional components mayrange from about 0.001% to about 10%.

Non-limiting examples of optional components for use in the compositioninclude cationic polymers, conditioning agents (hydrocarbon oils, fattyesters, silicones), anti dandruff agents, suspending agents, viscositymodifiers, dyes, nonvolatile solvents or diluents (water soluble andinsoluble), pearlescent aids, foam boosters, additional surfactants ornonionic cosurfactants, pediculocides, pH adjusting agents, perfumes,preservatives, chelants, proteins, skin active agents, sunscreens, UVabsorbers, vitamins, minerals, herbal/fruit/food extracts, sphingolipidsderivatives or synthetical derivative, and clay.

1. Cationic Polymers

The compositions of the present invention may contain a cationicpolymer. Concentrations of the cationic polymer in the compositiontypically range from about 0.05% to about 3%, preferably from about0.075% to about 2.0%, more preferably from about 0.1% to about 1.0%.Preferred cationic polymers will have cationic charge densities of atleast about 0.9 meq/gm, preferably at least about 1.2 meq/gm, morepreferably at least about 1.5 meq/gm, but also preferably less thanabout 7 meq/gm, more preferably less than about 5 meq/gm, at the pH ofintended use of the composition, which pH will generally range fromabout pH 3 to about pH 9, preferably between about pH 4 and about pH 8.Herein, “cationic charge density” of a polymer refers to the ratio ofthe number of positive charges on the polymer to the molecular weight ofthe polymer. The average molecular weight of such suitable cationicpolymers will generally be between about 10,000 and 10 million,preferably between about 50,000 and about 5 million, more preferablybetween about 100,000 and about 3 million.

Suitable cationic polymers for use in the compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. The cationicprotonated amines can be primary, secondary, or tertiary amines(preferably secondary or tertiary), depending upon the particularspecies and the selected pH of the composition. Any anionic counterionscan be used in association with the cationic polymers so long as thepolymers remain soluble in water, in the composition, or in a coacervatephase of the composition, and so long as the counterions are physicallyand chemically compatible with the essential components of thecomposition or do not otherwise unduly impair product performance,stability or aesthetics. Non limiting examples of such counterionsinclude halides (e.g., chloride, fluoride, bromide, iodide), sulfate andmethylsulfate.

Non limiting examples of such polymers are described in the CTFACosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley,and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

Non limiting examples of suitable cationic polymers include copolymersof vinyl monomers having cationic protonated amine or quaternaryammonium functionalities with water soluble spacer monomers such asacrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl anddialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinylcaprolactone or vinyl pyrrolidone.

Suitable cationic protonated amino and quaternary ammonium monomers, forinclusion in the cationic polymers of the composition herein, includevinyl compounds substituted with dialkylaminoalkyl acrylate,dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammoniumsalt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammoniumsalts, and vinyl quaternary ammonium monomers having cyclic cationicnitrogen-containing rings such as pyridinium, imidazolium, andquaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinylpyridinium, alkyl vinyl pyrrolidone salts.

Other suitable cationic polymers for use in the compositions includecopolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt(e.g., chloride salt) (referred to in the industry by the Cosmetic,Toiletry, and Fragrance Association, “CTFA”, as Polyquaternium-16);copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate(referred to in the industry by CTFA as Polyquaternium-1); cationicdiallyl quaternary ammonium-containing polymers, including, for example,dimethyldiallylammonium chloride homopolymer, copolymers of acrylamideand dimethyldiallylammonium chloride (referred to in the industry byCTFA as Polyquaternium 6 and Polyquaternium 7, respectively); amphotericcopolymers of acrylic acid including copolymers of acrylic acid anddimethyldiallylammonium chloride (referred to in the industry by CTFA asPolyquaternium 22), terpolymers of acrylic acid withdimethyldiallylammonium chloride and acrylamide (referred to in theindustry by CTFA as Polyquaternium 39), and terpolymers of acrylic acidwith methacrylamidopropyl trimethylammonium chloride and methylacrylate(referred to in the industry by CTFA as Polyquaternium 47). Preferredcationic substituted monomers are the cationic substituteddialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, andcombinations thereof. These preferred monomers conform the to theformula

wherein R¹ is hydrogen, methyl or ethyl; each of R², R³ and R⁴ areindependently hydrogen or a short chain alkyl having from about 1 toabout 8 carbon atoms, preferably from about 1 to about carbon atoms,more preferably from about 1 to about 2 carbon atoms; n is an integerhaving a value of from about 1 to about 8, preferably from about 1 toabout 4; and X is a counterion. The nitrogen attached to R², R³ and R⁴may be a protonated amine (primary, secondary or tertiary), but ispreferably a quaternary ammonium wherein each of R², R³ and R⁴ are alkylgroups a non limiting example of which is polymethyacrylamidopropyltrimonium chloride, available under the trade name Polycare 133, fromRhone-Poulenc, Cranberry, N.J., U.S.A.

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, such as cationic cellulose derivatives andcationic starch derivatives. Suitable cationic polysaccharide polymersinclude those which conform to the formula

wherein A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual; R is an alkylene oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1,R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms, and the total number of carbon atoms for each cationicmoiety (i.e., the sum of carbon atoms in R1, R2 and R3) preferably beingabout 20 or less; and X is an anionic counterion as described inhereinbefore.

Preferred cationic cellulose polymers are salts of hydroxyethylcellulose reacted with trimethyl ammonium substituted epoxide, referredto in the industry (CTFA) as Polyquaternium 10 and available fromAmerchol Corp. (Edison, N.J., USA) in their Polymer LR, JR, and KGseries of polymers. Other suitable types of cationic cellulose includesthe polymeric quaternary ammonium salts of hydroxyethyl cellulosereacted with lauryl dimethyl ammonium-substituted epoxide referred to inthe industry (CTFA) as Polyquaternium 24. These materials are availablefrom Amerchol Corp. under the tradename Polymer LM-200.

Other suitable cationic polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride, specific examples of whichinclude the Jaguar series commercially available from Rhone-PoulencIncorporated and the N-Hance series commercially available from AqualonDivision of Hercules, Inc. Other suitable cationic polymers includequaternary nitrogen-containing cellulose ethers, some examples of whichare described in U.S. Pat. No. 3,962,418. Other suitable cationicpolymers include copolymers of etherified cellulose, guar and starch,some examples of which are described in U.S. Pat. No. 3,958,581. Whenused, the cationic polymers herein are either soluble in the compositionor are soluble in a complex coacervate phase in the composition formedby the cationic polymer and the anionic, amphoteric and/or zwitterionicdetersive surfactant component described hereinbefore. Complexcoacervates of the cationic polymer can also be formed with othercharged materials in the composition.

Techniques for analysis of formation of complex coacervates are known inthe art. For example, microscopic analyses of the compositions, at anychosen stage of dilution, can be utilized to identify whether acoacervate phase has formed. Such coacervate phase will be identifiableas an additional emulsified phase in the composition. The use of dyescan aid in distinguishing the coacervate phase from other insolublephases dispersed in the composition.

2. Nonionic Polymers

Polyalkylene glycols having a molecular weight of more than about 1000are useful herein. Useful are those having the following generalformula:

wherein R⁹⁵ is selected from the group consisting of H, methyl, andmixtures thereof. Polyethylene glycol polymers useful herein are PEG-2M(also known as Polyox WSR® N-10, which is available from Union Carbideand as PEG-2,000); PEG-SM (also known as Polyox WSR® N-35 and PolyoxWSR® N-80, available from Union Carbide and as PEG-5,000 andPolyethylene Glycol 300,000); PEG-7M (also known as Polyox WSR® N-750available from Union Carbide); PEG-9M (also known as Polyox WSR® N-3333available from Union Carbide); and PEG-14 M (also known as Polyox WSR®N-3000 available from Union Carbide).

3. Conditioning Agents

Conditioning agents include any material which is used to give aparticular conditioning benefit to hair and/or skin. In hair treatmentcompositions, suitable conditioning agents are those which deliver oneor more benefits relating to shine, softness, combability, antistaticproperties, wet-handling, damage, manageability, body, and greasiness.The conditioning agents useful in the compositions of the presentinvention typically comprise a water insoluble, water dispersible,non-volatile, liquid that forms emulsified, liquid particles. Suitableconditioning agents for use in the composition are those conditioningagents characterized generally as silicones (e.g., silicone oils,cationic silicones, silicone gums, high refractive silicones, andsilicone resins), organic conditioning oils (e.g., hydrocarbon oils,polyolefins, and fatty esters) or combinations thereof, or thoseconditioning agents which otherwise form liquid, dispersed particles inthe aqueous surfactant matrix herein. Such conditioning agents should bephysically and chemically compatible with the essential components ofthe composition, and should not otherwise unduly impair productstability, aesthetics or performance.

The concentration of the conditioning agent in the composition should besufficient to provide the desired conditioning benefits, and as will beapparent to one of ordinary skill in the art. Such concentration canvary with the conditioning agent, the conditioning performance desired,the average size of the conditioning agent particles, the type andconcentration of other components, and other like factors.

1. Silicones

The conditioning agent of the compositions of the present invention ispreferably an insoluble silicone conditioning agent. The siliconeconditioning agent particles may comprise volatile silicone,non-volatile silicone, or combinations thereof. Preferred arenon-volatile silicone conditioning agents. If volatile silicones arepresent, it will typically be incidental to their use as a solvent orcarrier for commercially available forms of non-volatile siliconematerials ingredients, such as silicone gums and resins. The siliconeconditioning agent particles may comprise a silicone fluid conditioningagent and may also comprise other ingredients, such as a silicone resinto improve silicone fluid deposition efficiency or enhance glossiness ofthe hair.

The concentration of the silicone conditioning agent typically rangesfrom about 0.01% to about 10%, preferably from about 0.1% to about 8%,more preferably from about 0.1% to about 5%, more preferably from about0.2% to about 3%. Non-limiting examples of suitable siliconeconditioning agents, and optional suspending agents for the silicone,are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646,and U.S. Pat. No. 5,106,609. The silicone conditioning agents for use inthe compositions of the present invention preferably have a viscosity,as measured at 25° C., from about 20 to about 2,000,000 centistokes(“csk”), more preferably from about 1,000 to about 1,800,000 csk, evenmore preferably from about 50,000 to about 1,500,000 csk, morepreferably from about 100,000 to about 1,500,000 csk.

The dispersed silicone conditioning agent particles typically have anumber average particle diameter ranging from about 0.01 μm to about 50μm. For small particle application to hair, the number average particlediameters typically range from about 0.01 μm to about 4 μm, preferablyfrom about 0.01 μm to about 2 μm, more preferably from about 0.01 μm toabout 0.5 μm. For larger particle application to hair, the numberaverage particle diameters typically range from about 4 μm to about 50μm, preferably from about 6 μm to about 30 μm, more preferably fromabout 9 μm to about 20 μm, more preferably from about 12 μm to about 18μm.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, are foundin Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989).

a. Silicone Oils

Silicone fluids include silicone oils, which are flowable siliconematerials having a viscosity, as measured at 25° C., less than 1,000,000csk, preferably from about 5 csk to about 1,000,000 csk, more preferablyfrom about 100 csk to about 600,000 csk. Suitable silicone oils for usein the compositions of the present invention include polyalkylsiloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyethersiloxane copolymers, and mixtures thereof. Other insoluble, non-volatilesilicone fluids having hair conditioning properties may also be used.

Silicone oils include polyalkyl or polyaryl siloxanes which conform tothe following Formula (III):

wherein R is aliphatic, preferably alkyl or alkenyl, or aryl, R can besubstituted or unsubstituted, and x is an integer from 1 to about 8,000.Suitable R groups for use in the compositions of the present inventioninclude, but are not limited to: alkoxy, aryloxy, alkaryl, arylalkyl,arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, andhalogen-substituted aliphatic and aryl groups. Suitable R groups alsoinclude cationic amines and quaternary ammonium groups.

Preferred alkyl and alkenyl substituents are C₁ to C₅ alkyls andalkenyls, more preferably from C₁ to C₄, more preferably from C₁ to C₂.The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containinggroups (such as alkoxy, alkaryl, and alkamino) can be straight orbranched chains, and are preferably from C₁ to C₅, more preferably fromC₁ to C₄, even more preferably from C₁ to C₃, more preferably from C₁ toC₂. As discussed above, the R substituents can also contain aminofunctionalities (e.g. alkamino groups), which can be primary, secondaryor tertiary amines or quaternary ammonium. These include mono-, di- andtri-alkylamino and alkoxyamino groups, wherein the aliphatic portionchain length is preferably as described herein.

b. Amino and Cationic Silicones

Cationic silicone fluids suitable for use in the compositions of thepresent invention include, but are not limited to, those which conformto the general formula (V):

(R₁)_(a)G_(3-a)-Si—(OSiG₂)_(n)—(—OSiG_(b)(R₁)_(2-b)m)—O—SiG_(3-a)(R₁)_(a)

wherein G is hydrogen, phenyl, hydroxy, or C₁-C₈ alkyl, preferablymethyl; a is 0 or an integer having a value from 1 to 3, preferably 0; bis 0 or 1, preferably 1; n is a number from 0 to 1,999, preferably from49 to 499; m is an integer from 1 to 2,000, preferably from 1 to 10; thesum of n and m is a number from 1 to 2,000, preferably from 50 to 500;R₁ is a monovalent radical conforming to the general formula CqH_(2q)L,wherein q is an integer having a value from 2 to 8 and L is selectedfrom the following groups:

-   -   —N(R₂)CH₂—CH₂—N(R₂)₂    -   —N(R₂)₂    -   —N(R₂)₃A⁻    -   —N(R₂)CH₂—CH₂—NR₂H₂A⁻        wherein R₂ is hydrogen, phenyl, benzyl, or a saturated        hydrocarbon radical, preferably an alkyl radical from about C₁        to about C₂₀, and A⁻ is a halide ion.

An especially preferred cationic silicone corresponding to formula (V)is the polymer known as “trimethylsilylamodimethicone”, which is shownbelow in formula (VI):

Other silicone cationic polymers which may be used in the compositionsof the present invention are represented by the general formula (VII):

wherein R³ is a monovalent hydrocarbon radical from C₁ to C₁₈,preferably an alkyl or alkenyl radical, such as methyl; R₄ is ahydrocarbon radical, preferably a C₁ to C₁₈ alkylene radical or a C₁₀ toC₁₈ alkyleneoxy radical, more preferably a C₁ to C₈ alkyleneoxy radical;Q⁻ is a halide ion, preferably chloride; r is an average statisticalvalue from 2 to 20, preferably from 2 to 8; s is an average statisticalvalue from 20 to 200, preferably from 20 to 50. A preferred polymer ofthis class is known as UCARE SILICONE ALE 56™, available from UnionCarbide.

c. Silicone Gums

Other silicone fluids suitable for use in the compositions of thepresent invention are the insoluble silicone gums. These gums arepolyorganosiloxane materials having a viscosity, as measured at 25° C.,of greater than or equal to 1,000,000 csk. Silicone gums are describedin U.S. Pat. No. 4,152,416; Noll and Walter, Chemistry and Technology ofSilicones, New York: Academic Press (1968); and in General ElectricSilicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76.Specific non-limiting examples of silicone gums for use in thecompositions of the present invention include polydimethylsiloxane,(polydimethylsiloxane) (methylvinylsiloxane) copolymer,poly(dimethylsiloxane) (diphenyl siloxane)(methyl-vinylsiloxane)copolymer and mixtures thereof.

d. High Refractive Index Silicones

Other non-volatile, insoluble silicone fluid conditioning agents thatare suitable for use in the compositions of the present invention arethose known as “high refractive index silicones,” having a refractiveindex of at least about 1.46, preferably at least about 1.48, morepreferably at least about 1.52, more preferably at least about 1.55. Therefractive index of the polysiloxane fluid will generally be less thanabout 1.70, typically less than about 1.60. In this context,polysiloxane “fluid” includes oils as well as gums.

The high refractive index polysiloxane fluid includes those representedby general Formula (III) above, as well as cyclic polysiloxanes such asthose represented by Formula (VIII) below:

wherein R is as defined above, and n is a number from about 3 to about7, preferably from about 3 to about 5.

The high refractive index polysiloxane fluids contain an amount ofaryl-containing R substituents sufficient to increase the refractiveindex to the desired level, which is described herein. Additionally, Rand n must be selected so that the material is non-volatile.

Aryl-containing substituents include those which contain alicyclic andheterocyclic five and six member aryl rings and those which containfused five or six member rings. The aryl rings themselves can besubstituted or unsubstituted.

Generally, the high refractive index polysiloxane fluids will have adegree of aryl-containing substituents of at least about 15%, preferablyat least about 20%, more preferably at least about 25%, even morepreferably at least about 35%, more preferably at least about 50%.Typically, the degree of aryl substitution will be less than about 90%,more generally less than about 85%, preferably from about 55% to about80%.

Preferred high refractive index polysiloxane fluids have a combinationof phenyl or phenyl derivative substituents (more preferably phenyl),with alkyl substituents, preferably C₁-C₄ alkyl (more preferablymethyl), hydroxy, or C₁-C₄ alkylamino (especially —R¹NHR²NH2 whereineach R¹ and R² independently is a C₁-C₃ alkyl, alkenyl, and/or alkoxy).

When high refractive index silicones are used in the compositions of thepresent invention, they are preferably used in solution with a spreadingagent, such as a silicone resin or a surfactant, to reduce the surfacetension by a sufficient amount to enhance spreading and thereby enhancethe glossiness (subsequent to drying) of hair treated with thecompositions.

Silicone fluids suitable for use in the compositions of the presentinvention are disclosed in U.S. Pat. No. 2,826,551, U.S. Pat. No.3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433, andSilicon Compounds, Petrarch Systems, Inc. (1984).

e. Silicone Resins

Silicone resins may be included in the silicone conditioning agent ofthe compositions of the present invention. These resins are highlycross-linked polymeric siloxane systems. The cross-linking is introducedthrough the incorporation of trifunctional and tetrafunctional silaneswith monofunctional or difunctional, or both, silanes during manufactureof the silicone resin.

Silicone materials and silicone resins in particular, can convenientlybe identified according to a shorthand nomenclature system known tothose of ordinary skill in the art as “MDTQ” nomenclature. Under thissystem, the silicone is described according to presence of varioussiloxane monomer units which make up the silicone. Briefly, the symbol Mdenotes the monofunctional unit (CH₃)₃SiO_(0.5); D denotes thedifunctional unit (CH₃)₂SiO; T denotes the trifunctional unit(CH₃)SiO_(1.5); and Q denotes the quadra- or tetra-functional unit SiO₂.Primes of the unit symbols (e.g. M′, D′, T′, and Q′) denote substituentsother than methyl, and must be specifically defined for each occurrence.

Preferred silicone resins for use in the compositions of the presentinvention include, but are not limited to MQ, MT, MTQ, MDT and MDTQresins. Methyl is a preferred silicone substituent. Especially preferredsilicone resins are MQ resins, wherein the M:Q ratio is from about0.5:1.0 to about 1.5:1.0 and the average molecular weight of thesilicone resin is from about 1000 to about 10,000.

The weight ratio of the non-volatile silicone fluid, having refractiveindex below 1.46, to the silicone resin component, when used, ispreferably from about 4:1 to about 400:1, more preferably from about 9:1to about 200:1, more preferably from about 19:1 to about 100:1,particularly when the silicone fluid component is a polydimethylsiloxanefluid or a mixture of polydimethylsiloxane fluid andpolydimethylsiloxane gum as described herein. Insofar as the siliconeresin forms a part of the same phase in the compositions hereof as thesilicone fluid, i.e. the conditioning active, the sum of the fluid andresin should be included in determining the level of siliconeconditioning agent in the composition.

2. Organic Conditioning Oils

The conditioning component of the compositions of the present inventionmay also comprise from about 0.05% to about 3%, preferably from about0.08% to about 1.5%, more preferably from about 0.1% to about 1%, of atleast one organic conditioning oil as the conditioning agent, eitheralone or in combination with other conditioning agents, such as thesilicones (described herein).

a. Hydrocarbon Oils

Suitable organic conditioning oils for use as conditioning agents in thecompositions of the present invention include, but are not limited to,hydrocarbon oils having at least about 10 carbon atoms, such as cyclichydrocarbons, straight chain aliphatic hydrocarbons (saturated orunsaturated), and branched chain aliphatic hydrocarbons (saturated orunsaturated), including polymers and mixtures thereof. Straight chainhydrocarbon oils preferably are from about C₁₂ to about C₁₉. Branchedchain hydrocarbon oils, including hydrocarbon polymers, typically willcontain more than 19 carbon atoms.

Specific non-limiting examples of these hydrocarbon oils includeparaffin oil, mineral oil, saturated and unsaturated dodecane, saturatedand unsaturated tridecane, saturated and unsaturated tetradecane,saturated and unsaturated pentadecane, saturated and unsaturatedhexadecane, polybutene, polydecene, and mixtures thereof. Branched-chainisomers of these compounds, as well as of higher chain lengthhydrocarbons, can also be used, examples of which include highlybranched, saturated or unsaturated, alkanes such as thepermethyl-substituted isomers, e.g., the permethyl-substituted isomersof hexadecane and eicosane, such as2,2,4,4,6,6,8,8-dimethyl-10-methylundecane and2,2,4,4,6,6-dimethyl-8-methylnonane, available from PermethylCorporation. Hydrocarbon polymers such as polybutene and polydecene. Apreferred hydrocarbon polymer is polybutene, such as the copolymer ofisobutylene and butene. A commercially available material of this typeis L-14 polybutene from Amoco Chemical Corporation. The concentration ofsuch hydrocarbon oils in the composition preferably range from about0.05% to about 20%, more preferably from about 0.08% to about 1.5%, andeven more preferably from about 0.1% to about 1%.

b. Polyolefins

Organic conditioning oils for use in the compositions of the presentinvention can also include liquid polyolefins, more preferably liquidpoly-α-olefins, more preferably hydrogenated liquid poly-α-olefins.Polyolefins for use herein are prepared by polymerization of C₄ to aboutC₁₄ olefenic monomers, preferably from about C₆ to about C₁₂.

Non-limiting examples of olefenic monomers for use in preparing thepolyolefin liquids herein include ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,branched chain isomers such as 4-methyl-1-pentene, and mixtures thereof.Also suitable for preparing the polyolefin liquids are olefin-containingrefinery feedstocks or effluents. Preferred hydrogenated α-olefinmonomers include, but are not limited to: 1-hexene to 1-hexadecenes,1-octene to 1-tetradecene, and mixtures thereof.

c. Fatty Esters

Other suitable organic conditioning oils for use as the conditioningagent in the compositions of the present invention include, but are notlimited to, fatty esters having at least 10 carbon atoms. These fattyesters include esters with hydrocarbyl chains derived from fatty acidsor alcohols (e.g. mono-esters, polyhydric alcohol esters, and di- andtri-carboxylic acid esters). The hydrocarbyl radicals of the fattyesters hereof may include or have covalently bonded thereto othercompatible functionalities, such as amides and alkoxy moieties (e.g.,ethoxy or ether linkages, etc.).

Specific examples of preferred fatty esters include, but are not limitedto: isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexylpalmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecylstearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate,lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyloleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyladipate.

Other fatty esters suitable for use in the compositions of the presentinvention are mono-carboxylic acid esters of the general formula R′COOR,wherein R′ and R are alkyl or alkenyl radicals, and the sum of carbonatoms in R′ and R is at least 10, preferably at least 22.

Still other fatty esters suitable for use in the compositions of thepresent invention are di- and tri-alkyl and alkenyl esters of carboxylicacids, such as esters of C₄ to C₈ dicarboxylic acids (e.g. C₁ to C₂₂esters, preferably C₁ to C₆, of succinic acid, glutaric acid, and adipicacid). Specific non-limiting examples of di- and tri-alkyl and alkenylesters of carboxylic acids include isocetyl stearyol stearate,diisopropyl adipate, and tristearyl citrate.

Other fatty esters suitable for use in the compositions of the presentinvention are those known as polyhydric alcohol esters. Such polyhydricalcohol esters include alkylene glycol esters, such as ethylene glycolmono and di-fatty acid esters, diethylene glycol mono- and di-fatty acidesters, polyethylene glycol mono- and di-fatty acid esters, propyleneglycol mono- and di-fatty acid esters, polypropylene glycol monooleate,polypropylene glycol 2000 monostearate, ethoxylated propylene glycolmonostearate, glyceryl mono- and di-fatty acid esters, polyglycerolpoly-fatty acid esters, ethoxylated glyceryl monostearate, 1,3-butyleneglycol monostearate, 1,3-butylene glycol distearate, polyoxyethylenepolyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylenesorbitan fatty acid esters.

Still other fatty esters suitable for use in the compositions of thepresent invention are glycerides, including, but not limited to, mono-,di-, and tri-glycerides, preferably di- and tri-glycerides, morepreferably triglycerides. For use in the compositions described herein,the glycerides are preferably the mono-, di-, and tri-esters of glyceroland long chain carboxylic acids, such as C₁₀ to C₂₂ carboxylic acids. Avariety of these types of materials can be obtained from vegetable andanimal fats and oils, such as castor oil, safflower oil, cottonseed oil,corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil,sesame oil, lanolin and soybean oil. Synthetic oils include, but are notlimited to, triolein and tristearin glyceryl dilaurate.

Other fatty esters suitable for use in the compositions of the presentinvention are water insoluble synthetic fatty esters. Some preferredsynthetic esters conform to the general Formula (IX):

wherein R¹ is a C₇ to C₉ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenylgroup, preferably a saturated alkyl group, more preferably a saturated,linear, alkyl group; n is a positive integer having a value from 2 to 4,preferably 3; and Y is an alkyl, alkenyl, hydroxy or carboxy substitutedalkyl or alkenyl, having from about 2 to about 20 carbon atoms,preferably from about 3 to about 14 carbon atoms. Other preferredsynthetic esters conform to the general Formula (X):

wherein R² is a C₈ to C₁₀ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenylgroup; preferably a saturated alkyl group, more preferably a saturated,linear, alkyl group; n and Y are as defined above in Formula (X).

Specific non-limiting examples of suitable synthetic fatty esters foruse in the compositions of the present invention include: P-43 (C₈-C₁₀triester of trimethylolpropane), MCP-684 (tetraester of 3,3diethanol-1,5 pentadiol), MCP 121 (C₈-C₁₀ diester of adipic acid), allof which are available from Mobil Chemical Company.

3. Other Conditioning Agents

Also suitable for use in the compositions herein are the conditioningagents described by the Procter & Gamble Company in U.S. Pat. Nos.5,674,478, and 5,750,122. Also suitable for use herein are thoseconditioning agents described in U.S. Pat. Nos. 4,529,586 (Clairol),4,507,280 (Clairol), 4,663,158 (Clairol), 4,197,865 (L'Oreal), 4,217,914(L'Oreal), 4,381,919 (L'Oreal), and 4,422,853 (L'Oreal).

4. Additional Components

The compositions of the present invention may further include a varietyof additional useful components. Preferred additional components includethose discussed below:

1. Other Anti-Microbial Actives

The compositions of the present invention may further include one ormore anti-fungal or anti-microbial actives in addition to the metalpyrithione salt actives. Suitable anti-microbial actives include coaltar, sulfur, whitfield's ointment, castellani's paint, aluminumchloride, gentian violet, octopirox (piroctone olamine), ciclopiroxolamine, undecylenic acid and it's metal salts, potassium permanganate,selenium sulfide, sodium thiosulfate, propylene glycol, oil of bitterorange, urea preparations, griseofulvin, 8-Hydroxyquinoline ciloquinol,thiobendazole, thiocarbamates, haloprogin, polyenes, hydroxypyridone,morpholine, benzylamine, allylamines (such as terbinafine), tea treeoil, clove leaf oil, coriander, palmarosa, berberine, thyme red,cinnamon oil, cinnamic aldehyde, citronellic acid, hinokitol, ichthyolpale, Sensiva SC-50, Elestab HP-100, azelaic acid, lyticase,iodopropynyl butylcarbamate (IPBC), isothiazalinones such as octylisothiazalinone and azoles, and combinations thereof. Preferredanti-microbials include itraconazole, ketoconazole, selenium sulfide andcoal tar.

a. Azoles

Azole anti-microbials include imidazoles such as benzimidazole,benzothiazole, bifonazole, butaconazole nitrate, climbazole,clotrimazole, croconazole, eberconazole, econazole, elubiol,fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole,lanoconazole, metronidazole, miconazole, neticonazole, omoconazole,oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole,thiazole, and triazoles such as terconazole and itraconazole, andcombinations thereof. When present in the composition, the azoleanti-microbial active is included in an amount from about 0.01% to about5%, preferably from about 0.1% to about 3%, and more preferably fromabout 0.3% to about 2%, by weight of the composition. Especiallypreferred herein is ketoconazole.

b. Selenium Sulfide

Selenium sulfide is a particulate anti-dandruff agent suitable for usein the anti-microbial compositions of the present invention, effectiveconcentrations of which range from about 0.1% to about 4%, by weight ofthe composition, preferably from about 0.3% to about 2.5%, morepreferably from about 0.5% to about 1.5%. Selenium sulfide is generallyregarded as a compound having one mole of selenium and two moles ofsulfur, although it may also be a cyclic structure that conforms to thegeneral formula Se_(x)S_(y), wherein x+y=8. Average particle diametersfor the selenium sulfide are typically less than 15 μm, as measured byforward laser light scattering device (e.g. Malvern 3600 instrument),preferably less than 10 μm. Selenium sulfide compounds are described,for example, in U.S. Pat. No. 2,694,668; U.S. Pat. No. 3,152,046; U.S.Pat. No. 4,089,945; and U.S. Pat. No. 4,885,107.

c. Sulfur

Sulfur may also be used as a particulate anti-microbial/anti-dandruffagent in the anti-microbial compositions of the present invention.Effective concentrations of the particulate sulfur are typically fromabout 1% to about 4%, by weight of the composition, preferably fromabout 2% to about 4%.

d. Keratolytic Agents

The present invention may further comprise one or more keratolyticagents such as Salicylic Acid.

Additional anti-microbial actives of the present invention may includeextracts of melaleuca (tea tree) and charcoal. The present invention mayalso comprise combinations of anti-microbial actives. Such combinationsmay include octopirox and zinc pyrithione combinations, pine tar andsulfur combinations, salicylic acid and zinc pyrithione combinations,octopirox and climbasole combinations, and salicylic acid and octopiroxcombinations, and mixtures thereof.

2. Hair Loss Prevention and Hair Growth Agents

The present invention may further comprise materials useful for hairloss prevention and hair growth stimulants or agents. Examples of suchagents are Anti-Androgens such as Propecia, Dutasteride, RU5884;Anti-Inflammatories such as Glucocortisoids, Macrolides, Macrolides;Anti-Microbials such as Zinc pyrithione, Ketoconazole, Seleniumsulfiled, Acne Treatments; Immunosuppressives such as FK-506,Cyclosporin; vasodilators such as minoxidil, Aminexil® and combinationsthereof.

3. Sensates

The present invention may further comprise topical sensate materialssuch as terpenes, vanilloids, alkyl amides, natural extracts andcombinations thereof. Terpenes can include menthol and derivatives suchas menthyl lactate, ethyl menthane carboxamide, andmenthoyxypropanediol. Other terpenes can include camphor, eucalyptol,carvone, thymol and combinations thereof. Vanilloids can includecapsaicin, zingerone, eugenol, and vanillyl butyl ether. Alkyl amidescan include spilanthol, hydroxy alpha-sanschool, pellitorine andcombinations thereof. Natural extracts can include peppermint oil,eucalyptol, rosemary oil, ginger oil, clove oil, capsicum, jambuextract, cinnamon oil, laricyl and combinations thereof. Additionaltopical sensate materials can include methyl salicylate, anethole,benzocaine, lidocane, phenol, benzyl nicotinate, nicotinic acid,cinnamic aldehyde, cinnamyl alcohol, piperine, and combinations thereof.

4. Humectant

The compositions of the present invention may contain a humectant. Thehumectants herein are selected from the group consisting of polyhydricalcohols, water soluble alkoxylated nonionic polymers, and mixturesthereof. The humectants, when used herein, are preferably used at levelsof from about 0.1% to about 20%, more preferably from about 0.5% toabout 5%.

Polyhydric alcohols useful herein include glycerin, sorbitol, propyleneglycol, butylene glycol, hexylene glycol, ethoxylated glucose,1,2-hexane diol, hexanetriol, dipropylene glycol, erythritol, trehalose,diglycerin, xylitol, maltitol, maltose, glucose, fructose, sodiumchondroitin sulfate, sodium hyaluronate, sodium adenosine phosphate,sodium lactate, pyrrolidone carbonate, glucosamine, cyclodextrin, andmixtures thereof.

Water soluble alkoxylated nonionic polymers useful herein includepolyethylene glycols and polypropylene glycols having a molecular weightof up to about 1000 such as those with CTFA names PEG-200, PEG-400,PEG-600, PEG-1000, and mixtures thereof.

5. Suspending Agent

The compositions of the present invention may further comprise asuspending agent at concentrations effective for suspendingwater-insoluble material in dispersed form in the compositions or formodifying the viscosity of the composition. Such concentrations rangefrom about 0.1% to about 10%, preferably from about 0.3% to about 5.0%.

Suspending agents useful herein include polymeric suspending agents suchas anionic polymers and nonionic polymers. Useful herein are vinylpolymers such as cross linked acrylic acid polymers with the CTFA nameCarbomer, cellulose derivatives and modified cellulose polymers such asmethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, nitro cellulose, sodium cellulose sulfate, sodiumcarboxymethyl cellulose, crystalline cellulose, cellulose powder,polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guargum, xanthan gum, arabia gum, tragacanth, galactan, carob gum, guar gum,karaya gum, carragheenin, pectin, agar, quince seed (Cydonia oblongaMill), starch (rice, corn, potato, wheat), algae colloids (algaeextract), microbiological polymers such as dextran, succinoglucan,pulleran, starch-based polymers such as carboxymethyl starch,methylhydroxypropyl starch, alginic acid-based polymers such as sodiumalginate, alginic acid propylene glycol esters, acrylate polymers suchas sodium polyacrylate, polyethylacrylate, polyacrylamide,polyethyleneimine, and inorganic water soluble material such asbentonite, aluminum magnesium silicate, laponite, hectonite, andanhydrous silicic acid.

Commercially available viscosity modifiers highly useful herein includeCarbomers with tradenames Carbopol 934, Carbopol 940, Carbopol 950,Carbopol 980, and Carbopol 981, all available from B.F. GoodrichCompany, acrylates/steareth-20 methacrylate copolymer with tradenameACRYSOL 22 available from Rohm and Hass, nonoxynyl hydroxyethylcellulosewith tradename AMERCELL POLYMER HM-1500 available from Amerchol,methylcellulose with tradename BENECEL, hydroxyethyl cellulose withtradename NATROSOL, hydroxypropyl cellulose with tradename KLUCEL, cetylhydroxyethyl cellulose with tradename POLYSURF 67, all supplied byHercules, ethylene oxide and/or propylene oxide based polymers withtradenames CARBOWAX PEGs, POLYOX WASRs, and UCON FLUIDS, all supplied byAmerchol.

Other optional suspending agents include crystalline suspending agentswhich can be categorized as acyl derivatives, long chain amine oxides,and mixtures thereof. These suspending agents are described in U.S. Pat.No. 4,741,855. These preferred suspending agents include ethylene glycolesters of fatty acids preferably having from about 16 to about 22 carbonatoms. More preferred are the ethylene glycol stearates, both mono anddistearate, but particularly the distearate containing less than about7% of the mono stearate. Other suitable suspending agents includealkanol amides of fatty acids, preferably having from about 16 to about22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferredexamples of which include stearic monoethanolamide, stearicdiethanolamide, stearic monoisopropanolamide and stearicmonoethanolamide stearate. Other long chain acyl derivatives includelong chain esters of long chain fatty acids (e.g., stearyl stearate,cetyl palmitate, etc.); long chain esters of long chain alkanol amides(e.g., stearamide diethanolamide distearate, stearamide monoethanolamidestearate); and glyceryl esters (e.g., glyceryl distearate,trihydroxystearin, tribehenin) a commercial example of which is Thixin Ravailable from Rheox, Inc. Long chain acyl derivatives, ethylene glycolesters of long chain carboxylic acids, long chain amine oxides, andalkanol amides of long chain carboxylic acids in addition to thepreferred materials listed above may be used as suspending agents.

Other long chain acyl derivatives suitable for use as suspending agentsinclude N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof(e.g., Na, K), particularly N,N-di(hydrogenated) C.sub.16, C.sub.18 andtallow amido benzoic acid species of this family, which are commerciallyavailable from Stepan Company (Northfield, Ill., USA).

Examples of suitable long chain amine oxides for use as suspendingagents include alkyl dimethyl amine oxides, e.g., stearyl dimethyl amineoxide.

Other suitable suspending agents include primary amines having a fattyalkyl moiety having at least about 16 carbon atoms, examples of whichinclude palmitamine or stearamine, and secondary amines having two fattyalkyl moieties each having at least about 12 carbon atoms, examples ofwhich include dipalmitoylamine or di(hydrogenated tallow)amine. Stillother suitable suspending agents include di(hydrogenated tallow)phthalicacid amide, and crosslinked maleic anhydride-methyl vinyl ethercopolymer.

6. Other Optional Components

The compositions of the present invention may contain also vitamins andamino acids such as: water soluble vitamins such as vitamin B1, B2, B6,B12, C, pantothenic acid, pantothenyl ethyl ether, panthenol, biotin,and their derivatives, water soluble amino acids such as asparagine,alanin, indole, glutamic acid and their salts, water insoluble vitaminssuch as vitamin A, D, E, and their derivatives, water insoluble aminoacids such as tyrosine, tryptamine, and their salts.

The compositions of the present invention may also contain pigmentmaterials such as inorganic, nitroso, monoazo, disazo, carotenoid,triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine,anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine,botanical, natural colors, including: water soluble components such asthose having C. I. Names.

The compositions of the present invention may also contain antimicrobialagents which are useful as cosmetic biocides and antidandruff agentsincluding: water soluble components such as piroctone olamine, waterinsoluble components such as 3,4,4′-trichlorocarbanilide (triclocarban),triclosan and zinc pyrithione.

The compositions of the present invention may also contain chelatingagents.

H. COORDINATING COMPOUND HAVING A LOG Zn BINDING CONSTANT

In an embodiment of the present invention, the composition furthercomprises a coordinating compound with a Log Zn binding constant in arange sufficient to maintain zinc bioavailability. Preferably, such acoordinating compound has a Log Zn binding constant less than about 6,preferably less than about 5, more preferable less than about 4, andgreater than about −0.5. Preferably such a coordinating compound is anorganic acid, strong mineral acid, or coordinating species. Preferredexamples of such coordinating compounds include the following(respective Log Zn Binding Constant indicated in parenthesis): EDTA(16.5), EDDS (13.5), EDDA (11.1), NTA (10.7), Xylenol Orange (10.3),Cysteine (9.1), Cystine (6.7), Aspartic Acid (Aspartate) (5.9), Glycine(5.0), Citric Acid (Citrate) (4.8), Glutamic Acid (4.5), Methionine(4.4), Arginine (4.2), Carbonic Acid (Carbonate) (3.9), Ornithine (3.8),Tatronic Acid (Tartrate) (3.2), Malic Acid (Malate) (2.9), Malonic Acid(Malonate) (2.9), Tartaric Acid (Tartrate) (2.7), Adipic Acid (Adipate)(2.6), Phosphoric Acid (Phosphate) (2.4), Phthalic Acid (Phthalate)(2.2), Glycolic Acid (Glycolate) (2.0), Lactic Acid (Lactate) (1.9),Succinic Acid (Succinate) (1.8), Acetic Acid (Acetate) (1.0), SulfuricAcid (Sulfate) (0.9), Boric Acid (Borate) (0.9), Formic Acid (Formate)(0.6), Chloride (−0.3).

I. pH

In embodiments of the present invention, the pH may be in a range offrom about 6.5 to about 12, preferably from about 6.7 to about 9, morepreferably from about 6.8 to about 8.2, even more preferably from about7.0 to about 8.0. In preferred embodiments, the pH of the presentinvention may be greater than about 6.5, more preferably greater thanabout 6.8, and still more preferably, greater than about 7.

In an embodiment of the present invention, the graph in FIG. 1demonstrates the relationship between pH and percent (%) soluble zinc.An acid level study is demonstrated wherein solubility and pH aremeasured in a composition. As the pH goes below 7.5, the % soluble zincmeasured in a composition begins to rise. In the data below, citric acidappears to dissolve more zinc in the composition when compared tohydrochloric acid (HCl), on a weight basis.

J. CLASSIFICATION OF ZINC-CONTAINING MATERIALS ACCORDING TO THEIR ZINCAVAILABILITY

Zinc-containing materials (ZCMs) differ with respect to how strongly thezinc ion (Zn²⁺) is held by counterions in the crystal lattice. Thebenefits discussed herein depend upon having available Zn²⁺. Todetermine which ZCMs provide sufficient labile Zn²⁺ and those that donot, a test was developed using a metallochromic dye which changes colorupon coordinating Zn²⁺. The response is a binary visual assessment ofwhether or not the color changes indicating zinc-binding. If the colorchanges, the ZCM is classified as having available Zn²⁺ whereas if itdoes not change, the ZCM is not useful for this invention.

The method is based on the commercial metallochromic dye zincon. Zinconchanges from an orange color to blue upon binding zinc and provides thebasis for detecting available Zn²⁺:

The specific procedure involves making a stock solution of zincon inethanol (˜50 mg/10 ml ethanol). The ZCM is then added to water (˜30mg/10 ml water) and agitated (pH range should be 7-11). Three to fourdrops of zincon solution are then added to the ZCM in water, agitatedand a visual assessment of color change made.

Using this methodology, the following ZCM are examples of those thathave available zinc: zinc chloride, zinc sulfate, zinc citrate, zincoxide, zinc acetate, zinc stearate, zinc lactate, zinc salicylate, zincarginine, zinc histadine, zinc hexaborate, zinc hydroxide, zinc oxalate,zinc monoglycerolate and the like. Examples of ZCM not having availableZn²⁺ are zinc EDTA, zinc sulfide, zinc phytate and other materials withvery tightly bound zinc.

In an embodiment of the present invention, the composition comprisesfrom 5% to 50% of a surfactant; a zinc containing material wherein zincavailability is measured by a zinc ion reacting with a metallochromicdye zincon to give a dye color change from orange to blue. In anotherembodiment of the present invention, the composition comprises from 5%to 50% of a surfactant; a zinc containing material wherein zincavailability is measured by a zinc ion reacting with a metallochromicdye zincon to give a dye color change from orange to blue; and a zincionophore.

K. METHOD FOR ASSESSMENT OF ZINC LABILITY IN ZINC-CONTAINING PRODUCTS

Zinc lability is a measure of the chemical availability of zinc ion.Soluble zinc salts that do not complex with other species in solutionhave a relative zinc lability, by definition, of 100%. The use ofpartially soluble forms of zinc salts and/or incorporation in a matrixwith potential complexants generally lowers the zinc labilitysubstantially below the defined 100% maximum.

Zinc lability is assessed by combining a diluted zinc-containingsolution or dispersion with the metallochromic dye xylenol orange (XO)and measurement of the degree of color change under specifiedconditions. The magnitude of color formation is proportional to thelevel of labile zinc. The procedure developed has been optimized foraqueous surfactant formulations but may be adapted to other physicalproduct forms as well.

A spectrophotometer is used to quantify the color change at 572 nm, thewavelength of optimum color change for XO. The spectrophotometer is setto zero absorbance at 572 nm utilizing a product control as close incomposition to the test product except excluding the potentially labileform of zinc. The control and test products are then treated identicallyas follows. A 50 μl product sample is dispensed into a jar and 95 ml ofdeaerated, distilled water are added and stirred. 5 mL of a 23 mg/mLxylenol orange stock solution at pH 5.0 is pipetted into the sample jar;this is considered time 0. The pH is then adjusted to 5.50±0.01 usingdilute HCl or NaOH. After 10.0 minutes, a portion of the sample isfiltered (0.45μ) and the absorbance measured at 572 nm. The measuredabsorbance is then compared to a separately measured control todetermine the relative zinc lability (zero TO 100%). The 100% labilitycontrol is prepared in a matrix similar to the test products bututilizing a soluble zinc material (such as zinc sulfate) incorporated atan equivalent level on a zinc basis. The absorbance of the 100% labilitycontrol is measured as above for the test materials. The relative zinclability is preferably greater than about 15%, more preferably greaterthan about 20%, and even more preferably greater than about 25%.

Using this methodology, the below examples demonstrate a material(hydrozincite) that has intrinsically high lability in an anionicsurfactant system compared to one (ZnO) with low intrinsic lability. Theexamples further demonstrate that the low lability of ZnO can beimproved substantially by incorporating a protective material such assodium bicarbonate, a source of carbonate anions and mixtures thereof:

Relative Zinc Lability (%) Simple Surfactant Simple Surfactant System¹Plus System¹ Alone Sodium Bicarbonate² Zinc Oxide 1.5 33.2 Hydrozincite37.0 ¹Simple surfactant system: 6% sodium lauryl sulfate ²Addition ofsodium bicarbonate: 0.2% level

L. METHODS OF MANUFACTURE FOR SHAMPOO COMPOSITIONS

The compositions of the present invention may be prepared by any knownor otherwise effective technique, suitable for providing ananti-microbial composition provided that the resulting compositionprovides the excellent anti-microbial benefits described herein. Methodsfor preparing the anti-dandruff and conditioning shampoo embodiments ofthe present invention include conventional formulation and mixingtechniques. A method such as that described in U.S. Pat. No. 5,837,661,could be employed, wherein the anti-microbial agent of the presentinvention would typically be added in the same step as the siliconepremix is added in the U.S. Pat. No. 5,837,661 description.

M. METHODS OF USE

The compositions of the present invention may be used in directapplication to the skin or in a conventional manner for cleansing skinand hair and controlling microbial infection (including fungal, viral,or bacterial infections) on the skin or scalp. The compositions hereinare useful for cleansing the hair and scalp, and other areas of the bodysuch as underarm, feet, and groin areas and for any other area of skinin need of treatment. The present invention may be used for treating orcleansing of the skin or hair of animals as well. An effective amount ofthe composition, typically from about 1 g to about 50 g, preferably fromabout 1 g to about 20 g of the composition, for cleansing hair, skin orother area of the body, is topically applied to the hair, skin or otherarea that has preferably been wetted, generally with water, and thenrinsed off. Application to the hair typically includes working theshampoo composition through the hair.

A preferred method for providing anti-microbial (especiallyanti-dandruff) efficacy with a shampoo embodiment comprises the stepsof: (a) wetting the hair with water, (b) applying an effective amount ofthe anti-microbial shampoo composition to the hair, and (c) rinsing theanti-microbial shampoo composition from the hair using water. Thesesteps may be repeated as many times as desired to achieve the cleansing,conditioning, and anti-microbial/anti-dandruff benefits sought.

It is also contemplated that when the anti-microbial active employed iszinc pyrithione, and/or if other optional hair growth regulating agentsare employed, the anti-microbial compositions of the present invention,may, provide for the regulation of growth of the hair. The method ofregularly using such shampoo compositions comprises repeating steps a,b, and c (above).

A further embodiment of the present invention comprises a methodcomprising the steps of (a) wetting the hair with water, (b) applying aneffective amount of a shampoo composition comprising a zinc ionophore,(c) rinsing the shampoo compositions from the hair using water; (d)applying an effective amount of a conditioner composition comprising azinc containing material according to the present invention; (e) rinsingthe conditioner composition from the hair using water. In a furtherembodiment, this method could be conducted wherein steps d and b arereversed. In a further embodiment, steps b and d can vary and be ashampoo, hair lotions, hair sprays, hair tonics, conditioningtreatments, gels, mousses and dressings, and the like. A preferredembodiment of the above mentioned method includes a shampoo compositioncomprising zinc pyrithione and a conditioner composition comprising zincoxide.

A further embodiment of the present invention comprises a method oftreating athlete's foot comprising the use of the composition accordingto the present invention, a method of treating microbial infectionscomprising the use of composition as described herein, method ofimproving the appearance of a scalp comprising the use of thecomposition according present invention, a method of treating fungalinfections comprising the use of the composition according to thepresent invention, a method of treating dandruff comprising the use ofthe composition of the present invention, a method of treating diaperdermatitis and candidiasis comprising the use of the compositions of thepresent invention as described herein, a method of treating tineacapitis comprising the use of the composition according to the presentinvention, a method of treating yeast infections comprising the use ofthe composition according to the present invention, a method of treatingonychomycosis comprising the use of the composition according to thepresent invention.

N. EXAMPLES

The following examples further describe and demonstrate the preferredembodiments within the scope of the present invention. The examples aregiven solely for the purpose of illustration, and are not to beconstrued as limitations of the present invention since many variationsthereof are possible without departing from its scope.

The composition of the invention can be made by mixing one or moreselected metal ion sources and one or more metal salts of pyrithione inan appropriate media or carrier, or by adding the individual componentsseparately to the skin or hair cleansing compositions. Useful carriersare discussed more fully above.

1. Topical Compositions

All exemplified compositions can be prepared by conventional formulationand mixing techniques. Component amounts are listed as weight percentsand exclude minor materials such as diluents, filler, and so forth. Thelisted formulations, therefore, comprise the listed components and anyminor materials associated with such components. As used herein,“minors” refers to those optional components such as preservatives,viscosity modifiers, pH modifiers, fragrances, foam boosters, and thelike. As is apparent to one of ordinary skill in the art, the selectionof these minors will vary depending on the physical and chemicalcharacteristics of the particular ingredients selected to make thepresent invention as described herein. Other modifications can beundertaken by the skilled artisan without departing from the spirit andscope of this invention. These exemplified embodiments of theanti-microbial shampoo, anti-microbial cleansing compositions,anti-microbial cleansing/facial compositions of the present inventionprovide excellent anti-microbial efficacy.

Antimicrobial Shampoo Examples 1-54

A suitable method for preparing the anti-microbial shampoo compositionsdescribed in Examples 1-54 (below) follows:

About one-third to all of the sodium laureth sulfate (added as 25 wt %solution) and acid are added to a jacketed mix tank and heated to about60° C. to about 80° C. with slow agitation to form a surfactantsolution. The pH of this solution is about 7.5. Sodium benzoate,Cocoamide MEA and fatty alcohols, (where applicable), are added to thetank and allowed to disperse. Ethylene glycol distearate (“EGDS”) isadded to the mixing vessel and allowed to melt (where applicable). Afterthe EGDS is melted and dispersed, Kathon CG is added to the surfactantsolution. The resulting mixture is cooled to about 25° C. to about 40°C. and collected in a finishing tank. As a result of this cooling step,the EGDS crystallizes to form a crystalline network in the product(where applicable). The remainder of the sodium laureth sulfate andother components, including the silicone and anti-microbial agent(s),are added to the finishing tank with agitation to ensure a homogeneousmixture. Polymers (cationic or nonionic) are dispersed in water or oilsas an about 0.1% to about 10% dispersion and/or solution and then addedto the final mix. ZnO or Zinc Hydroxy carbonate (“ZHC”) can be added toa premix of surfactants or water with or without the aid of a dispersingagent via conventional powder incorporation and mixing techniques intothe final mix. Adjustment of ZnO particle size can be affected byvarious conventional mixing techniques obvious to one skilled in theart. Once all components have been added, additional viscosity modifiersmay be added, as needed, to the mixture to adjust product viscosity tothe extent desired.

Shampoo Compositions - Examples 1-10 Example Example Example ExampleExample Example Example Example Example Example Components 1 2 3 4 5 6 78 9 10 Sodium Laureth Sulfate 10.00 10.00 10.00 10.00 10.00 10.00 10.0010.00 10.00 10.00 Sodium Lauryl Sulfate 6.00 6.00 6.00 6.00 6.00 6.006.00 6.00 6.00 6.00 Cocamidopropyl Betaine Sodium Cocoisethionate EGDS1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 0.8000.800 0.800 0.800 0.800 0.800 0.800 1.600 Cetyl Alcohol 0.600 0.6000.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 Guar Hydroxy Propyl0.500 0.500 0.500 0.500 0.500 0.500 0.500 0.500 0.500 0.500 TrimoniumChloride (1) Guar Hydroxy Propyl Trimonium Chloride (2) Guar HydroxyPropyl Trimonium Chloride (3) Polyquaterium-10 (4) Polyquaterium-10 (5)PEG-7M (6) PEG-14M (7) PEG-45M (8) Dimethicone (9) 0.85 0.85 0.85 0.850.85 0.85 0.85 0.85 0.85 0.85 Dimethicone (10) ZPT (11) 1.00 2.00 2.001.00 1.00 1.00 1.00 1.00 1.00 1.00 Zinc Oxide 1.20 1.20 0.60 0.60 0.301.20 1.20 1.20 1.20 1.20 Zinc Hydroxy Carbonate Sodium Bicarbonate 0.200.20 0.20 0.20 0.20 0.10 0.05 0.25 0.20 Hydrochloric Acid 0.78 0.78 0.780.78 0.78 0.53 0.40 0.91 0.28 0.78 Magnesium Sulfate 0.28 0.28 0.28 0.280.28 0.28 0.28 0.28 0.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.8000.800 0.800 0.800 0.800 0.800 0.800 Sodium Xylenesulfonate Perfume 0.7500.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 Sodium Benzoate0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 Kathon0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.02250.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. %Maximum XO Lability 63.2% 38.9% 38.5% 63.9% 23.5% 88.8% % Soluble Zinc0.024 0.017 2.55 × 5.01 × 0.011 10⁻³ 10⁻³ (1) Guar having a molecularweight of about 400,000, and having a charge density of about 0.84meq/g, available from Aqualon. (2) Guar having a molecular weight ofabout 400,000, and having a charge density of about 2.0 meq/g, availablefrom Aqualon. (3) Cationic guar Jaguar C17 available from Rhodia (4)Polymer JR30M available from Amerchol (5) Polymer LR400 available fromAmerchol (6) Polyox WSR N-750 available from Amerchol (7) Polyox WSRN-3000 available from Amerchol (8) Polyox WSR N-60K available fromAmerchol (9) Viscasil 330M available from General Electric Silicones(10) DC1664 available from Dow Corning Silicones (11) ZPT having anaverage particle size of about 2.5 μm, available from Arch/Olin.

Shampoo Compositions - Examples 11-20 Example Example Example ExampleExample Example Example Example Example Example Components 11 12 13 1415 16 17 18 19 20 Sodium Laureth Sulfate 10.00 10.00 10.00 10.00 10.0012.50 10.00 10.00 10.00 10.00 Sodium Lauryl Sulfate 6.00 6.00 6.00 6.006.00 1.50 6.00 6.00 6.00 6.00 Cocamidopropyl Betaine 2.00 2.70 SodiumCocoisethionate EGDS 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50CMEA 1.600 0.800 0.800 1.600 0.800 0.800 0.800 0.800 0.800 0.800 CetylAlcohol 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 GuarHydroxy Propyl 0.500 0.500 0.500 0.500 0.500 0.500 0.500 0.500 TrimoniumChloride (1) Guar Hydroxy Propyl 0.500 Trimonium Chloride (2) GuarHydroxy Propyl 0.500 Trimonium Chloride (3) Polyquaterium-10 (4)Polyquaterium-10 (5) PEG-7M (6) 0.200 0.200 PEG-14M (7) PEG-45M (8)0.200 Dimethicone (9) 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85Dimethicone (10) ZPT (11) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Zinc Oxide1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 0.60 0.30 Zinc Hydroxy CarbonateSodium Bicarbonate 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Hydrochloric Acid0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.28 0.28 0.28 Magnesium Sulfate 0.280.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 Sodium Chloride 0.800 0.8000.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 Sodium XylenesulfonatePerfume 0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750Sodium Benzoate 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.2500.250 Kathon 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.00080.0008 0.0008 Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.0225 0.02250.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. Q.S. % Maximum XO Lability 59.8% 58.2% 72.9% 71.7% 67.2% %Soluble Zinc (1) Guar having a molecular weight of about 400,000, andhaving a charge density of about 0.84 meq/g, available from Aqualon. (2)Guar having a molecular weight of about 400,000, and having a chargedensity of about 2.0 meq/g, available from Aqualon. (3) Cationic guarJaguar C17 available from Rhodia (4) Polymer JR30M available fromAmerchol (5) Polymer LR400 available from Amerchol (6) Polyox WSR N-750available from Amerchol (7) Polyox WSR N-3000 available from Amerchol(8) Polyox WSR N-60K available from Amerchol (9) Viscasil 330M availablefrom General Electric Silicones (10) DC1664 available from Dow CorningSilicones (11) ZPT having an average particle size of about 2.5 μm,available from Arch/Olin.

Shampoo Compositions - Examples 21-30 Example Example Example ExampleExample Example Example Example Example Example Components 21 22 23 2425 26 27 28 29 30 Sodium Laureth Sulfate 10.00 10.00 10.00 10.00 10.0010.00 10.00 10.00 10.00 10.00 Sodium Lauryl Sulfate 6.00 6.00 6.00 6.006.00 6.00 6.00 6.00 6.00 6.00 Cocamidopropyl Betaine SodiumCocoisethionate EGDS 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50CMEA 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 CetylAlcohol 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 GuarHydroxy Propyl 0.500 0.400 0.250 0.500 0.500 0.500 0.500 0.500 0.500Trimonium Chloride (1) Guar Hydroxy Propyl Trimonium Chloride (2) GuarHydroxy Propyl Trimonium Chloride (3) Polyquaterium-10 (4)Polyquaterium-10 (5) 0.500 0.500 0.100 PEG-7M (6) 0.100 0.100 PEG-14M(7) PEG-45M (8) Dimethicone (9) 0.85 1.40 0.85 0.85 0.85 0.85 1.35 1.000.85 0.85 Dimethicone (10) ZPT (11) 1.00 1.00 1.00 1.00 1.00 0.50 1.001.00 2.00 2.00 Zinc Oxide 1.20 1.20 1.20 1.20 Zinc Hydroxy Carbonate1.61 1.61 1.61 1.61 1.61 0.80 Sodium Bicarbonate 0.20 0.20 0.20 0.20Hydrochloric Acid 0.78 0.78 0.78 0.78 0.42 0.42 0.42 0.42 0.42 0.42Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28Sodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.8000.800 Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.750 0.750 0.7500.750 0.750 0.750 0.750 Sodium Benzoate 0.250 0.250 0.250 0.250 0.2500.250 0.250 0.250 0.250 0.250 Kathon 0.0008 0.0008 0.0008 0.0008 0.00080.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol 0.0225 0.0225 0.02250.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. % Maximum XO Lability 74.0% % SolubleZinc 0.022 (1) Guar having a molecular weight of about 400,000, andhaving a charge density of about 0.84 meq/g, available from Aqualon. (2)Guar having a molecular weight of about 400,000, and having a chargedensity of about 2.0 meq/g, available from Aqualon. (3) Cationic guarJaguar C17 available from Rhodia (4) Polymer JR30M available fromAmerchol (5) Polymer LR400 available from Amerchol (6) Polyox WSR N-750available from Amerchol (7) Polyox WSR N-3000 available from Amerchol(8) Polyox WSR N-60K available from Amerchol (9) Viscasil 330M availablefrom General Electric Silicones (10) DC1664 available from Dow CorningSilicones (11) ZPT having an average particle size of about 2.5 μm,available from Arch/Olin.

Shampoo Compositions - Examples 31-40 Example Example Example ExampleExample Example Example Example Example Example Components 31 32 33 3435 36 37 38 39 40 Sodium Laureth Sulfate 10.00 10.00 10.00 10.00 10.0010.00 10.00 10.00 10.00 10.00 Sodium Lauryl Sulfate 6.00 6.00 6.00 6.006.00 6.00 6.00 6.00 6.00 6.00 Cocamidopropyl Betaine SodiumCocoisethionate EGDS 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50CMEA 0.800 0.800 1.600 0.800 0.800 1.600 0.800 0.800 0.800 0.800 CetylAlcohol 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 GuarHydroxy Propyl 0.500 0.500 0.500 0.500 0.500 0.500 0.500 TrimoniumChloride (1) Guar Hydroxy Propyl 0.500 Trimonium Chloride (2) GuarHydroxy Propyl 0.500 0.500 Trimonium Chloride (3) Polyquaterium-10 (4)Polyquaterium-10 (5) PEG-7M (6) 0.200 0.100 PEG-14M (7) 0.200 PEG-45M(8) 0.200 Dimethicone (9) 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85Dimethicone (10) 1.00 ZPT (11) 2.00 1.00 1.00 1.00 1.00 1.00 1.00 1.001.00 1.00 Zinc Oxide Zinc Hydroxy Carbonate 0.40 1.61 1.61 1.61 1.611.61 1.61 1.61 1.61 1.61 Sodium Bicarbonate Hydrochloric Acid 0.42 0.420.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 Magnesium Sulfate 0.28 0.28 0.280.28 0.28 0.28 0.28 0.28 0.28 0.28 Sodium Chloride 0.800 0.800 0.8000.800 0.800 0.800 0.800 0.800 0.800 0.800 Sodium Xylenesulfonate Perfume0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 SodiumBenzoate 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250Kathon 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.00080.0008 Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.02250.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. % Maximum XO Lability 65.6% 76.2% % Soluble Zinc (1) Guar having amolecular weight of about 400,000, and having a charge density of about0.84 meq/g, available from Aqualon. (2) Guar having a molecular weightof about 400,000, and having a charge density of about 2.0 meq/g,available from Aqualon. (3) Cationic guar Jaguar C17 available fromRhodia (4) Polymer JR30M available from Amerchol (5) Polymer LR400available from Amerchol (6) Polyox WSR N-750 available from Amerchol (7)Polyox WSR N-3000 available from Amerchol (8) Polyox WSR N-60K availablefrom Amerchol (9) Viscasil 330M available from General ElectricSilicones (10) DC1664 available from Dow Corning Silicones (11) ZPThaving an average particle size of about 2.5 μm, available fromArch/Olin.

Shampoo Compositions - Examples 41-50 Example Example Example ExampleExample Example Example Example Example Example Components 41 42 43 4445 46 47 48 49 50 Sodium Laureth Sulfate 10.00 12.50 10.00 10.00 10.0010.00 10.00 10.00 10.00 10.00 Sodium Lauryl Sulfate 6.00 1.50 6.00 6.006.00 6.00 6.00 6.00 6.00 6.00 Cocamidopropyl Betaine 2.00 2.70 SodiumCocoisethionate 2.00 EGDS 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.501.50 CMEA 0.800 0.800 0.800 1.600 1.600 0.800 0.800 0.800 0.800 0.800Cetyl Alcohol 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.6000.600 Guar Hydroxy Propyl 0.500 0.500 0.500 0.500 Trimonium Chloride (1)Guar Hydroxy Propyl Trimonium Chloride (2) Guar Hydroxy Propyl TrimoniumChloride (3) Polyquaterium-10 (4) 0.500 0.500 Polyquaterium-10 (5) 0.5000.500 0.500 0.250 PEG-7M (6) 0.200 0.100 0.100 PEG-14M (7) PEG-45M (8)Dimethicone (9) 0.85 0.85 0.85 0.85 1.40 1.40 1.40 1.40 0.85 0.85Dimethicone (10) ZPT (11) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.001.00 Zinc Oxide Zinc Hydroxy Carbonate 1.61 1.61 1.61 1.61 1.61 1.611.61 1.61 1.61 1.61 Sodium Bicarbonate Hydrochloric Acid 0.42 0.42 0.420.42 0.42 0.42 0.42 0.42 0.42 0.42 Magnesium Sulfate 0.28 0.28 0.28 0.280.28 0.28 0.28 0.28 0.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.8000.800 0.800 0.800 0.800 0.800 0.800 Sodium Xylenesulfonate Perfume 0.7500.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 0.750 Sodium Benzoate0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 Kathon0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.02250.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. %Maximum XO Lability 66.7% 66.9% % Soluble Zinc (1) Guar having amolecular weight of about 400,000, and having a charge density of about0.84 meq/g, available from Aqualon. (2) Guar having a molecular weightof about 400,000, and having a charge density of about 2.0 meq/g,available from Aqualon. (3) Cationic guar Jaguar C17 available fromRhodia (4) Polymer JR30M available from Amerchol (5) Polymer LR400available from Amerchol (6) Polyox WSR N-750 available from Amerchol (7)Polyox WSR N-3000 available from Amerchol (8) Polyox WSR N-60K availablefrom Amerchol (9) Viscasil 330M available from General ElectricSilicones (10) DC1664 available from Dow Corning Silicones (11) ZPThaving an average particle size of about 2.5 μm, available fromArch/Olin.

Shampoo Compositions - Examples 51-54 Example Example Example ExampleExample Components 51 52 53 54A 54B Sodium Laureth Sulfate 10.00 10.0010.00 10.00 10.00 Sodium Lauryl Sulfate 6.00 6.00 6.00 6.00 6.00Cocamidopropyl Betaine Sodium Cocoisethionate EGDS 1.50 1.50 1.50 1.501.50 CMEA 0.800 0.800 0.800 0.800 0.800 Cetyl Alcohol 0.600 0.600 0.6000.600 0.600 Guar Hydroxy Propyl 0.400 0.500 Trimonium Chloride (1) GuarHydroxy Propyl 0.500 0.500 0.500 Trimonium Chloride (2) Guar HydroxyPropyl Trimonium Chloride (3) Polyquaterium-10 (4) Polyquaterium-10 (5)0.100 PEG-7M (6) 0.100 PEG-14M (7) PEG-45M (8) Dimethicone (9) 0.85 0.850.85 0.85 0.85 Dimethicone (10) ZPT (11) 1.00 Zinc Oxide Zinc HydroxyCarbonate 1.61 1.61 0.80 0.40 1.61 Sodium Bicarbonate Fumaric Acid 0.53Hydrochloric Acid 0.42 0.42 0.42 0.42 Magnesium Sulfate 0.28 0.28 0.280.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.800 SodiumXylenesulfonate Perfume 0.750 0.750 0.750 0.750 0.750 Sodium Benzoate0.250 0.250 0.250 0.250 0.250 Kathon 0.0008 0.0008 0.0008 0.0008 0.0008Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S.Q.S. Q.S. % Maximum XO Lability % Soluble Zinc (1) Guar having amolecular weight of about 400,000, and having a charge density of about0.84 meq/g, available from Aqualon. (2) Guar having a molecular weightof about 400,000, and having a charge density of about 2.0 meq/g,available from Aqualon. (3) Cationic guar Jaguar C17 available fromRhodia (4) Polymer JR30M available from Amerchol (5) Polymer LR400available from Amerchol (6) Polyox WSR N-750 available from Amerchol (7)Polyox WSR N-3000 available from Amerchol (8) Polyox WSR N-60K availablefrom Amerchol (9) Viscasil 330M available from General ElectricSilicones (10) DC1664 available from Dow Corning Silicones (11) ZPThaving an average particle size of about 2.5 μm, available fromArch/Olin.

Cleansing Compositions Examples 55-61

A suitable method for preparing the anti-microbial cleansingcompositions described in Examples 55-61 (below) follows:

Components 1-3, 9, and 10 are mixed with heating to 190F. Components 4,12, 15 and 17 are mixed at room temperature in a separate pot. After thefirst mixture has reached 190F, it is added to the second mixture. Afterthis mixture has cooled below 140 F, components 13 (& 5) is added. In aseparate vessel at 160 F, the petrolatum and ZnO or ZHC are mixed. Whenthe aqueous phase has cooled below 110 F, the petrolatum/ZnO or ZHCblend is added and agitated until smooth. ZnO or ZHC can also be addedto a premix of surfactants or water with or without the aid of adispersing agent via conventional powder incorporation and mixingtechniques into the cooled mixture. Adjustment of ZnO particle size canbe affected by various conventional mixing techniques obvious to oneskilled in the art. Finally the perfume is added.

Example Example Example Example Example Example Example Components 55 5657 58 59 60 61 1 Sodium Lauryl Sulfate 4.000 4.000 4.000 4.000 4.0004.000 4.000 2 Sodium Laureth Sulfate 3.000 3.000 3.000 3.000 3.000 3.0003.000 3 Sodium Laruroamphoacetate 4.000 4.000 4.000 4.000 4.000 4.0004.000 4 Sodium Lauroyl Sarcosinate 2.000 2.000 2.000 2.000 2.000 2.0002.000 5 Zinc Pyrithione (1) 1.000 6 Zinc Oxide treated with 2.000 6.0006.000 silicone (2) 7 Zinc Oxide 2.000 5.000 8 Zinc Hydroxy Carbonate2.000 4.000 9 Lauric Acid 1.000 1.000 1.000 1.000 1.000 1.000 1.000 10Trihydroxystearin 0.650 0.650 0.650 0.650 0.650 0.650 0.650 11 CitricAcid as needed as needed as needed as needed as needed as needed asneeded 12 Sodium Benzoate 0.250 0.250 0.250 0.250 0.250 0.250 0.250 13Glydant 0.120 0.120 0.120 0.120 0.120 0.120 0.120 14 Perfume 0.750 0.7500.750 0.750 0.750 0.750 0.750 15 Polyquaterium-10 (3) 0.750 0.750 0.7500.750 0.750 0.750 0.750 16 Petrolatum 15.000 15.000 15.000 15.000 15.00015.000 15.000 17 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. (1) ZPT havingan average particle size of about 2.5 μm, available from Arch/Olin. (2)Z-Cote HP-1 available from BASF (3) Polymer JR30M available fromAmerchol

Cleansing/Facial Compositions Examples 62-75

A suitable method for preparing the anti-microbial cleansing/facialcompositions described in Examples 62-75 are known to those skilled inthe art, and may be prepared by any known or otherwise effectivetechnique, suitable for providing an anti-microbial cleansing/facialcomposition provided that the resulting composition provides theexcellent anti-microbial benefits described herein. Methods forpreparing the anti-microbial cleansing/facial compositions embodimentsof the present invention include conventional formulation and mixingtechniques. A method such as that described in U.S. Pat. No. 5,665,364,could be employed.

Example Example Example Example Example Example Example Components 62 6364 65 66 67 68 Cetyl Betaine 6.667 6.667 6.667 6.667 6.667 6.667 6.667PPG-15 Stearyl Ether 4.000 4.000 4.000 4.000 4.000 4.000 4.000 SodiumLauryl Sulfate 3.571 3.571 3.571 3.571 3.571 3.571 3.571Distearyldimonium Chloride Glycerin 3.000 3.000 3.000 3.000 3.000 3.0003.000 Stearyl Alcohol 2.880 2.880 2.880 2.880 2.880 2.880 2.880Distearyldimonium Chloride 1.500 1.500 1.500 1.500 1.500 1.500 1.500Oxidized Polyethylene 1.000 1.000 1.000 1.000 1.000 1.000 1.000 ZincPyrithione (1) 1.000 Zinc Oxide 1.200 0.600 0.300 1.200 Zinc HydroxyCarbonate 1.610 0.800 0.400 Cetyl Alcohol 0.800 0.800 0.800 0.800 0.8000.800 0.800 Steareth-21 0.500 0.500 0.500 0.500 0.500 0.500 0.500Behenyl Alcohol 0.320 0.320 0.320 0.320 0.320 0.320 0.320 PPG-30 0.2500.250 0.250 0.250 0.250 0.250 0.250 Steareth-2 0.250 0.250 0.250 0.2500.250 0.250 0.250 Perfume 0.200 0.200 0.200 0.200 0.200 0.200 0.200Citric Acid As Needed As Needed As Needed As Needed As Needed As NeededAs Needed Sodium Citrate As Needed As Needed As Needed As Needed AsNeeded As Needed As Needed Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Example Example Example Example Example Example Example Components 69 7071 72 73 74 75 Sodium Laureth Sulfate 8.000 8.000 8.000 8.000 8.0008.000 8.000 Disodium 7.000 7.000 7.000 7.000 7.000 7.000 7.000Cocamphodiacetate PEG-80 Glyceryl Cocoate 3.500 3.500 3.500 3.500 3.5003.500 3.500 Sodium Chloride 2.170 2.170 2.170 2.170 2.170 2.170 2.170Glycol Distearate 2.000 2.000 2.000 2.000 2.000 2.000 2.000 ZincPyrithione (1) 1.000 Zinc Oxide 1.200 0.600 0.300 1.200 Zinc HydroxyCarbonate 1.610 0.800 0.400 Dimethicone 0.900 0.900 0.900 0.900 0.9000.900 0.900 Sodium Trideceth-7 0.502 0.502 0.502 0.502 0.502 0.502 0.502Carboxylate Perfume 0.320 0.320 0.320 0.320 0.320 0.320 0.320 CitricAcid As needed As needed As needed As needed As needed As needed Asneeded Quaternium-15 0.150 0.150 0.150 0.150 0.150 0.150 0.150Polyquaterium-10 0.150 0.150 0.150 0.150 0.150 0.150 0.150 PEG-30Glyceryl Cocoate As Needed As Needed As Needed As Needed As Needed AsNeeded As Needed Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. (1) ZPT havingan average particle size of about 2.5 μm, available from Arch/Olin.

10. Other Ingredients

The present invention may, in some embodiments, further compriseadditional optional components known or otherwise effective for use inhair care or personal care products. The concentration of such optionalingredients generally ranges from zero to about 25%, more typically fromabout 0.05% to about 20%, even more typically from about 0.1% to about15%, by weight of the composition. Such optional components should alsobe physically and chemically compatible with the essential componentsdescribed herein, and should not otherwise unduly impair productstability, aesthetics or performance.

Non-limiting examples of optional components for use in the presentinvention include anti-static agents, foam boosters, anti-dandruffagents in addition to the anti-dandruff agents described above,viscosity adjusting agents and thickeners, suspension materials (e.g.EGDS, thixins), pH adjusting agents (e.g. sodium citrate, citric acid,succinic acid, sodium succinate, sodium maleate, sodium glycolate, malicacid, glycolic acid, hydrochloric acid, sulfuric acid, sodiumbicarbonate, sodium hydroxide, and sodium carbonate), preservatives(e.g. DMDM hydantoin), anti-microbial agents (e.g. triclosan ortriclocarbon), dyes, organic solvents or diluents, pearlescent aids,perfumes, fatty alcohols, proteins, skin active agents, sunscreens,vitamins (such as retinoids including retinyl propionate, vitamin E suchas tocopherol acetate, panthenol, and vitamin B3 compounds includingniacinamide), emulsifiers, volatile carriers, select stability actives,styling polymers, organic styling polymers, silicone-grafted stylingpolymers, cationic spreading agents, pediculocides, foam boosters,viscosity modifiers and thickeners, polyalkylene glycols andcombinations thereof.

Optional anti-static agents such as water-insoluble cationic surfactantsmay be used, typically in concentrations ranging from about 0.1% toabout 5%, by weight of the composition. Such anti-static agents shouldnot unduly interfere with the in-use performance and end-benefits of theanti-microbial composition; particularly, the anti-static agent shouldnot interfere with the anionic surfactant. A specific non-limitingexample of a suitable anti-static agents is tricetyl methyl ammoniumchloride.

Optional foam boosters for use in the present invention described hereininclude fatty ester (e.g. C₈-C₂₂) mono- and di(C₁-C₅, especially C₁-C₃)alkanol amides. Specific non-limiting examples of such foam boostersinclude coconut monoethanolamide, coconut diethanolamide, and mixturesthereof.

Optional viscosity modifiers and thickeners may be used, typically inamounts effective for the anti-microbial compositions of the presentinvention to generally have an overall viscosity from about 1,000 csk toabout 20,000 csk, preferably from about 3,000 csk to about 10,000 csk.Specific non-limiting examples of such viscosity modifiers andthickeners include: sodium chloride, sodium sulfate, and mixturesthereof.

O. OTHER PREFERRED EMBODIMENTS

Other preferred embodiments of the present invention include thefollowing:

An embodiment of the present invention relates to a compositioncomprising 5% to 50% of a surfactant, an effective amount of a zinccontaining material and from 40% to 95% water. Preferably the zinccontaining material in having an aqueous solubility within thecomposition of less than about 25% by weight at 25° C. Preferably thezinc containing material for such a composition is an inorganicmaterial, natural zinc containing material, ore, mineral, organic salt,polymeric salt, physically adsorbed form material, or mixtures thereof.Preferably the inorganic material in such a composition is a zincaluminate, zinc carbonate, zinc oxide, calamine, zinc phosphate, zincselenide, zinc sulfide, zinc silicate, zinc silicofluoride, zinc borate,or zinc hydroxide, zinc hydroxy sulfate, or mixtures thereof. Preferablythe surfactant in such a composition is anionic, cationic, nonionic,amphoteric or zwitterionic surfactants, or mixtures thereof; morepreferably a mixture of an anionic surfactant and a zwitterionicsurfactant, or anionic surfactant and amphoteric surfactant.

Another embodiment of the present invention relates to a compositioncomprising from about 5% to about 50% of a surfactant; from about 0.001%to about 10% of zinc oxide; and a ZIM; wherein the pH of the compositionis greater than about 7; and wherein the ZIM is a zinc ionophore,hydrophobic zinc material, or mixtures thereof. Another embodiment ofthe present invention relates to a composition comprising from about 5%to about 50% of a surfactant; from about 0.001% to about 10% of zinchydroxycarbonate, and a ZIM; wherein the pH of the composition isgreater than about 7; and wherein the ZIM is a zinc ionophore,hydrophobic zinc material, or mixtures thereof. Preferably the ZIM insuch a composition is a polyvalent metal salt of pyrithione,dithiocarbamate, heterocyclic amine, nonsteriodal anti-inflammatorycompound, naturally occurring material having zinc ionophoric behavior,derivative of a naturally occurring material having zinc ionophoricbehavior, bio-molecule, pepetide, sulfur-based compound, transportenhancer, or mixtures thereof; more preferably a pyrithione or a zincsalt of pyrithione; more preferably still, zinc pyrithione. The pH ofsuch a composition is preferably from about 7.0 to 9. Preferably such acomposition comprises a compound having a having a Log zinc bindingconstant of less than about 6; preferably such a compound is an organicacid, strong mineral acid, zinc coordinating species, or mixturesthereof; more preferably the compound is sodium bicarbonate. Preferablythe surfactant in such a composition is anionic, cationic, nonionic,amphoteric, zwitterionic, or mixtures thereof. Preferably the zinccontaining material is present in such a composition in an amount of0.1% to about 3% by weight of the composition. Preferably such acomposition further comprises a conditioning agent. Preferably such acomposition further comprises a cationic deposition polymer.

In a preferred embodiment, the zinc containing material has a aqueoussolubility within a composition of less than about 25% by weight at 25°C.

In another embodiment of the present invention, the compositionembodiment may be employed to treat a variety of conditions, including:athlete's foot, microbial infections, improving the appearance of ascalp, treating fungal infections, treating dandruff, treating diaperdermatitis and candidiasis, treating tinea capitis, treating yeastinfections, treating onychomycosis. Preferably such conditions aretreated by applying a composition of the present invention to theaffected area.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A personal care method, comprising the step of topically applying apersonal care composition to areas of the body other than the scalp andhair growing therefrom, the personal care composition comprising: a. azinc containing material having an aqueous solubility within thecomposition of less than about 25% by weight at 25° C.; b. one or moresurfactants; and c. from about 40% to about 95% of added water, whereinthe pH of the composition is greater than about
 7. 2. The personal caremethod of claim 1, wherein the area of the body is the underarm.
 3. Thepersonal care method of claim 1, wherein the area of the body is thegroin and/or feet.
 4. The personal care method of claim 1, wherein thecomposition comprises from about 0.01% to about 5%, by weight of thecomposition, of the zinc containing material.
 5. The personal caremethod of claim 1, wherein the composition comprises from about 0.1% toabout 3%, by weight of the composition, of the zinc containing material.6. The personal care method of claim 1, wherein the zinc containingmaterial is selected from the group consisting of inorganic materials,natural zinc containing materials, ores, minerals, organic salts,polymeric salts, and mixtures thereof.
 7. The personal care method ofclaim 6, wherein the inorganic material comprises zinc oxide.
 8. Thepersonal care method of claim 7, wherein the composition furthercomprises a component selected from the group consisting of sodiumbicarbonate, sources of carbonate anions, and mixtures thereof.
 9. Thepersonal care method of claim 1, wherein the zinc containing material isa zinc-containing layered material.
 10. The personal care method ofclaim 9, wherein the zinc-containing layered material is selected fromthe group consisting of basic zinc carbonate hydroxide, zinc coppercarbonate, copper zinc carbonate hydroxide, phyllosilicate containingzinc ions, layered double hydroxide, hydroxy double salts, and mixturesthereof.
 11. The personal care method of claim 9, wherein thezinc-containing layered material is selected from the group consistingof zinc hydroxycarbonate, hydrozincite, basic zinc carbonate, andmixtures thereof.
 12. The personal care method of claim 9, wherien thezinc-containing layered material is hydrozincite or basic zinccarbonate.
 13. The personal care method of claim 1, wherein thecomposition is substantially free of zinc pyrithione.
 14. The personalcare method of claim 1, wherein the zinc containing material has arelative zinc lability of greater than about 15%.
 15. The personal caremethod of claim 1, wherein the zinc containing material has a relativezinc lability of greater than about 20%.
 16. The personal care method ofclaim 1, wherein the zinc containing material has a relative zinclability of greater than about 25%.
 17. A personal care method,comprising the step of topically applying a personal care composition tothe underarm, the personal care composition comprising: a. from about0.01% to about 5% of a zinc-containing layered material having anaqueous solubility within the composition of less than about 25% byweight at 25° C.; b. one or more surfactants; and c. from about 40% toabout 95% of added water, wherein the pH of the composition is greaterthan about
 7. 18. The personal care method of claim 17, wherein thezinc-containing layered material has a relative zinc lability of greaterthan about 15%.
 19. The personal care method of claim 17, wherein thezinc-containing layered material comprises hydrozincite and/or basiczinc carbonate.
 20. A personal care method, comprising the step oftopically applying a personal care composition to the groin and/or feet,the personal care composition comprising: a. from about 0.01% to about5% of a zinc-containing layered material having an aqueous solubilitywithin the composition of less than about 25% by weight at 25° C.; b.one or more surfactants; and c. from about 40% to about 95% of addedwater, wherein the pH of the composition is greater than about 7.